Diimine metal complex, method of preparation thereof, and use thereof

Abstract

The present invention relates to a diimine metal complex represented by Chemical Formula I, a method for preparing the same, and uses thereof. The complex is used as a main catalyst for olefin polymerization and can produce high molecular weight branched polyethylene by achieving catalytic ethylene polymerization at high temperatures. Chemical Formula I

Description

Technology Field

[0001] The present invention relates to a diimine-metal complex, a method for preparing the same, and uses thereof. Background Technology

[0002] Polyolefin resins are widely used in industrial and household goods due to their superior environmental friendliness compared to other resin materials. Polyethylene resin is an important polyolefin resin. Commercial polyethylene catalysts include Ziegler-Natta type catalysts (e.g., DE Pat 889229 (1953); IT Pat 545332 (1956) and IT Pat 536899 (1955); see Chem. Rev., 2000, 100, 1169 and related references), Phillips type catalysts (e.g., Belg. Pat. 530617 (1955); see Chem. Rev. 1996, 96, 3327), and metallocene type catalysts (e.g., see W. Kaminsky, Metalorganic Catalysts for Synthesis and Polymerization, Berlin: Springer, 1999), and late-transition metal complex type high-efficiency ethylene oligomerization and polymerization catalysts that have been rapidly developed in recent years. For example, in 1995, Brookhart et al. reported a class of α-diimine Ni(II) complexes capable of polymerizing ethylene at high activity.

[0003] α-diimide nickel catalysts have attracted considerable attention due to their high activity and the high tunability of the molecular weight and branching of the resulting polymers. Companies including DuPont have filed numerous patent applications (WO 96 / 23010, WO 98 / 03521, WO 98 / 40374, WO 99 / 05189, WO 99 / 62968, WO 00 / 06620, US 6,103,658, US 6,660,677). These α-diimide nickel catalysts can catalyze ethylene oligomerization or polymerization at high activity under the action of methylaluminoxane or aluminum alkyl at room temperature or low temperatures. However, when the reaction temperature increases above 50°C, the activity of these α-diimide nickel catalysts generally decreases sharply, and the molecular weight of the polyethylene produced decreases sharply as the polymerization temperature increases.

[0004] Conventional ethylene gas-phase polymerization processes generally require polymerization temperatures of 85°C or higher, and ethylene solution polymerization processes generally require polymerization temperatures of 130 to 250°C. Therefore, to meet the requirements of existing gas-phase and solution ethylene polymerization equipment, it is necessary to develop late-transition metal catalysts suitable for use at relatively high temperatures, such as 80°C or higher.

[0005] The inventors have conducted continuous research to overcome the disadvantages of the prior art. As a result, it was found that a class of diimine-metal complexes possesses excellent thermal stability. In particular, diimine-metal complexes can maintain higher ethylene polymerization activity even at higher temperatures, and the resulting polymer has a narrower molecular weight distribution.

[0006] The object of the present invention is to provide a dimine-metal complex represented by the chemical formula I:

[0007] Chemical Formula I

[0008] In the above chemical formula I, R1 and R2 are each independently C1-C30 hydrocarbyl having or not having substituent Q; R3 and R4 are each independently selected from the group consisting of hydrogen, halogen, hydroxyl, and C1-C20 hydrocarbyl having or not having substituent Q, and adjacent R3 and R4 groups are optionally connected to form a ring or ring system; and each R 11 is independently a C1-C20 hydrocarbyl with or without substituent Q; each Y is independently a Group VIA nonmetal atom; each M is independently a Group VIII metal; and each X is independently selected from the group consisting of a halogen, a C1-C10 hydrocarbyl with or without substituent Q, and a C1-C10 hydrocarbyloxy with or without substituent Q.

[0009] Another objective of the present invention is to provide a method for preparing a diimine-metal complex.

[0010] Another objective of the present invention is to provide a use of diimine-metal complexes in olefin polymerization.

[0011] Another object of the present invention is to provide an olefin polymerization method comprising carrying out an olefin polymerization reaction in the presence of a diimine-metal complex or a catalyst containing the same. Specific details for implementing the invention

[0012] In a first aspect, the present invention provides a diimine-metal complex represented by the formula I:

[0013] Chemical Formula I

[0014] In the above chemical formula I, R1 and R2 are each independently C1-C30 hydrocarbyl having or not having substituent Q; R3 and R4 are each independently selected from the group consisting of hydrogen, halogen, hydroxyl, and C1-C20 hydrocarbyl having or not having substituent Q, and adjacent R3 and R4 groups are optionally connected to form a ring or ring system; and each R 11 is independently a C1-C20 hydrocarbyl with or without substituent Q; each Y is independently a Group VIA nonmetal atom; each M is independently a Group VIII metal; and each X is independently selected from the group consisting of a halogen, a C1-C10 hydrocarbyl with or without substituent Q, and a C1-C10 hydrocarbyloxy with or without substituent Q.

[0015] In some embodiments, R1 and R2 are independently selected from the group consisting of C1-C20 alkyls having or not having substituent Q and C6-C20 aryls having or not having substituent Q.

[0016] In a preferred embodiment, R1 and / or R2 are groups represented by the formula A:

[0017] Chemical formula A

[0018] In the above chemical formula A, R 1 -R 5Each is independently selected from the group consisting of hydrogen, halogen, hydroxyl, C1-C20 alkyl having or not having substituent Q, C2-C20 alkenyl having or not having substituent Q, C2-C20 alkynyl having or not having substituent Q, C1-C20 alkoxy having or not having substituent Q, C2-C20 alkenoxy having or not having substituent Q, C2-C20 alkynoxy having or not having substituent Q, C6-C20 aryl having or not having substituent Q, C6-C20 aryloxy having or not having substituent Q, C7-C20 aralkyl having or not having substituent Q, C7-C20 aralkoxy having or not having substituent Q, C7-C20 alkaryl having or not having substituent Q, and C7-C20 alkaryloxy having or not having substituent Q, and R 1 -R 5 It is optionally connected to form a ring or ring system.

[0019] Preferably, in formula A, R 1 -R 5 Each independently hydrogen, halogen, hydroxy, C1-C10 alkyl having or not having substituent Q, C2-C10 alkenyl having or not having substituent Q, C2-C10 alkynyl having or not having substituent Q, C3-C10 cycloalkyl having or not having substituent Q, C1-C10 alkoxy having or not having substituent Q, C2-C10 alkenoxy having or not having substituent Q, C2-C10 alkynoxy having or not having substituent Q, C3-C10 cycloalkoxy having or not having substituent Q, C6-C15 aryl having or not having substituent Q, C6-C15 aryloxy having or not having substituent Q, C7-C15 aralkyl having or not having substituent Q, C7-C15 aralkoxy having or not having substituent Q, and having or not having substituent Q It is selected from the group consisting of C7-C15 alkalil and C7-C15 alkaliloxy having or not having substituent Q.

[0020] In some embodiments, each M is independently selected from the group consisting of nickel and palladium.

[0021] In some embodiments, each Y is independently selected from the group consisting of O and S.

[0022] In some embodiments, each X is independently selected from the group consisting of a halogen, a C1-C10 alkyl having or not having substituent Q, and a C1-C10 alkoxy having or not having substituent Q, and preferably selected from the group consisting of a halogen, a C1-C6 alkyl having or not having substituent Q, and a C1-C6 alkoxy having or not having substituent Q.

[0023] In some embodiments, each R 11 is independently a C1-C20 alkyl having or not having substituent Q, preferably a C1-C10 alkyl having or not having substituent Q, more preferably a C1-C6 alkyl having or not having substituent Q.

[0024] In some embodiments, R3 and R4 are each independently from the group consisting of hydrogen, halogen, hydroxyl, C1-C20 alkyl having or not having substituent Q, C2-C20 alkenyl having or not having substituent Q, C2-C20 alkynyl having or not having substituent Q, C1-C20 alkoxy having or not having substituent Q, C2-C20 alkenoxy having or not having substituent Q, C2-C20 alkynoxy having or not having substituent Q, C6-C20 aryl having or not having substituent Q, C6-C20 aryloxy having or not having substituent Q, C7-C20 aralkyl having or not having substituent Q, C7-C20 aralkoxy having or not having substituent Q, C7-C20 alkaryl having or not having substituent Q, and C7-C20 alkaryloxy having or not having substituent Q. It is selected. Preferably, R3 and R4 are each independently hydrogen, halogen, hydroxyl, C1-C10 alkyl having or not having substituent Q, C2-C10 alkenyl having or not having substituent Q, C2-C10 alkynyl having or not having substituent Q, C3-C10 cycloalkyl having or not having substituent Q, C1-C10 alkoxy having or not having substituent Q, C2-C10 alkenoxy having or not having substituent Q, C2-C10 alkynoxy having or not having substituent Q, C3-C10 cycloalkoxy having or not having substituent Q, C6-C15 aryl having or not having substituent Q, C6-C15 aryloxy having or not having substituent Q, C7-C15 aralkyl having or not having substituent Q, C7-C15 aralkoxy having or not having substituent Q, and having or not having substituent Q. It is selected from the group consisting of C7-C15 alkaline groups that do not have substituent Q and C7-C15 alkaline oxy groups that have or do not have substituent Q.More preferably, R3 and R4 are each independently selected from the group consisting of hydrogen, C1-C10 alkyl, halogenated C1-C10 alkyl, C1-C10 alkoxy, halogenated C1-C10 alkoxy, and halogen, and more preferably selected from the group consisting of hydrogen, C1-C6 alkyl, halogenated C1-C6 alkyl, C1-C6 alkoxy, halogenated C1-C6 alkoxy, and halogen.

[0025] In some embodiments, the substituent Q is selected from the group consisting of halogen, hydroxy, C1-C10 alkyl, halogenated C1-C10 alkyl, C1-C10 alkoxy, and halogenated C1-C10 alkoxy, and preferably selected from the group consisting of halogen, hydroxy, C1-C6 alkyl, halogenated C1-C6 alkyl, C1-C6 alkoxy, and halogenated C1-C6 alkoxy. Preferably, the C1-C6 alkyl is selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, isopentyl, n-hexyl, isohexyl, and 3,3-dimethylbutyl. Preferably, the C1-C6 alkoxy is selected from the group consisting of methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, iso-butoxy, n-pentoxy, iso-pentoxy, n-hexoxy, iso-hexoxy, and 3,3-dimethylbutoxy.

[0026] The term "halogen" used here refers to fluorine, chlorine, bromine, or iodine.

[0027] In some embodiments, the dimine-metal complex according to the present invention is as represented by Formula III:

[0028] Chemical Formula III

[0029] In the above chemical formula III, R 1 -R 5Each is independently selected from the group consisting of hydrogen, halogen, hydroxyl, C1-C10 alkyl having or not having substituent Q, C3-C10 cycloalkyl having or not having substituent Q, C1-C10 alkoxy having or not having substituent Q, C3-C10 cycloalkoxy having or not having substituent Q, C6-C15 aryl having or not having substituent Q, C7-C15 aralkyl having or not having substituent Q, and C7-C15 alkalil having or not having substituent Q;

[0030] R3 and R4 are each independently selected from the group consisting of hydrogen, C1-C10 alkyl, halogenated C1-C10 alkyl, C1-C10 alkoxy, halogenated C1-C10 alkoxy, and halogen, and more preferably selected from the group consisting of hydrogen, C1-C6 alkyl, halogenated C1-C6 alkyl, C1-C6 alkoxy, halogenated C1-C6 alkoxy, and halogen;

[0031] Each M is nickel;

[0032] Each Y is O and;

[0033] Each X is independently selected from the group consisting of fluorine, chlorine, and bromine;

[0034] Each R 11 is independently a C1-C20 alkyl having or not having substituent Q, preferably a C1-C10 alkyl having or not having substituent Q, more preferably a C1-C6 alkyl having or not having substituent Q;

[0035] Preferably, the substituent Q is independently selected from the group consisting of halogen, hydroxy, C1-C6 alkyl, halogenated C1-C6 alkyl, C1-C6 alkoxy, and halogenated C1-C6 alkoxy.

[0036] In a lower aspect, the dimine-metal complex according to the present invention is represented by the chemical formula Ia:

[0037] Chemical formula Ia

[0038] In the above chemical formula Ia, R5-R7 are each independently selected from the group consisting of hydrogen, halogen, hydroxyl, and C1-C20 hydrocarbyl having or not having substituent Q, and R5-R7 are optionally connected to form a ring or ring system; R1, R2, R 11 , Y, M and X are as defined above for chemical formula I.

[0039] In some embodiments of these sub-aspects, R1 and R2 are independently selected from the group consisting of C1-C20 alkyls having or not having substituent Q and C6-C20 aryls having or not having substituent Q. Preferably, R1 and / or R2 are groups represented by the formula A:

[0040] Chemical formula A

[0041] In the above chemical formula A, R 1 -R 5 Each is independently selected from the group consisting of hydrogen, halogen, hydroxyl, C1-C20 alkyl having or not having substituent Q, C2-C20 alkenyl having or not having substituent Q, C2-C20 alkynyl having or not having substituent Q, C1-C20 alkoxy having or not having substituent Q, C2-C20 alkenoxy having or not having substituent Q, C2-C20 alkynoxy having or not having substituent Q, C6-C20 aryl having or not having substituent Q, C6-C20 aryloxy having or not having substituent Q, C7-C20 aralkyl having or not having substituent Q, C7-C20 aralkoxy having or not having substituent Q, C7-C20 alkaryl having or not having substituent Q, and C7-C20 alkaryloxy having or not having substituent Q, and R 1 -R 5 are optionally connected to form a ring or ring system. Preferably, R1 -R 5 Each independently hydrogen, halogen, hydroxy, C1-C10 alkyl having or not having substituent Q, C2-C10 alkenyl having or not having substituent Q, C2-C10 alkynyl having or not having substituent Q, C3-C10 cycloalkyl having or not having substituent Q, C1-C10 alkoxy having or not having substituent Q, C2-C10 alkenoxy having or not having substituent Q, C2-C10 alkynoxy having or not having substituent Q, C3-C10 cycloalkoxy having or not having substituent Q, C6-C15 aryl having or not having substituent Q, C6-C15 aryloxy having or not having substituent Q, C7-C15 aralkyl having or not having substituent Q, C7-C15 aralkoxy having or not having substituent Q, and having or not having substituent Q It is selected from the group consisting of C7-C15 alkalil and C7-C15 alkaliloxy having or not having substituent Q.

[0042] In some embodiments of these sub-aspects, each M is independently selected from the group consisting of nickel and palladium.

[0043] In some implementations of these sub-aspects, each Y is independently selected from the group consisting of O and S.

[0044] In some embodiments of these sub-aspects, each X is independently selected from the group consisting of a halogen, a C1-C10 alkyl having or not having substituent Q, and a C1-C10 alkoxy having or not having substituent Q, and preferably selected from the group consisting of a halogen, a C1-C6 alkyl having or not having substituent Q, and a C1-C6 alkoxy having or not having substituent Q.

[0045] In some implementations of these sub-aspects, each R 11is independently a C1-C20 alkyl having or not having substituent Q, preferably a C1-C10 alkyl having or not having substituent Q, and more preferably a C1-C6 alkyl having or not having substituent Q.

[0046] In some embodiments of these sub-aspects, the substituent Q is selected from the group consisting of halogen, hydroxy, C1-C10 alkyl, halogenated C1-C10 alkyl, C1-C10 alkoxy, and halogenated C1-C10 alkoxy, and preferably selected from the group consisting of halogen, hydroxy, C1-C6 alkyl, halogenated C1-C6 alkyl, C1-C6 alkoxy, and halogenated C1-C6 alkoxy. Preferably, the C1-C6 alkyl is selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, isopentyl, n-hexyl, isohexyl, and 3,3-dimethylbutyl. Preferably, the C1-C6 alkoxy is selected from the group consisting of methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, iso-butoxy, n-pentoxy, iso-pentoxy, n-hexoxy, iso-hexoxy, and 3,3-dimethylbutoxy.

[0047] In some embodiments of these sub-aspects, the diimine-metal complex is as represented by the formula IIa:

[0048] Chemical formula IIa

[0049] In the above chemical formula IIa, R5-R 10Each is independently selected from the group consisting of hydrogen, halogen, hydroxy, C1-C20 alkyl having or not having substituent Q, C2-C20 alkenyl having or not having substituent Q, C2-C20 alkynyl having or not having substituent Q, C1-C20 alkoxy having or not having substituent Q, C2-C20 alkenoxy having or not having substituent Q, C2-C20 alkynoxy having or not having substituent Q, C6-C20 aryl having or not having substituent Q, C6-C20 aryloxy having or not having substituent Q, C7-C20 aralkyl having or not having substituent Q, C7-C20 aralkoxy having or not having substituent Q, C7-C20 alkaryl having or not having substituent Q, and C7-C20 alkaryloxy having or not having substituent Q.

[0050] R1, R2, M, X, Y, and R 11 is as defined above for chemical formula Ia.

[0051] In some embodiments of these sub-aspects, R5-R7 in Formula Ia and R5-R7 in Formula IIa 10Each is independently hydrogen, halogen, hydroxyl, C1-C10 alkyl having or not having substituent Q, C2-C10 alkenyl having or not having substituent Q, C2-C10 alkynyl having or not having substituent Q, C3-C10 cycloalkyl having or not having substituent Q, C1-C10 alkoxy having or not having substituent Q, C2-C10 alkenoxy having or not having substituent Q, C2-C10 alkynoxy having or not having substituent Q, C3-C10 cycloalkoxy having or not having substituent Q, C6-C15 aryl having or not having substituent Q, C6-C15 aryloxy having or not having substituent Q, C7-C15 aralkyl having or not having substituent Q, C7-C15 aralkoxy having or not having substituent Q, and having or not having substituent Q It is selected from the group consisting of C7-C15 alkalil and C7-C15 alkaliloxy having or not having substituent Q. Preferably, R5-R7 of Formula Ia and R5-R7 of Formula IIa. 10 Each is independently selected from the group consisting of hydrogen, C1-C10 alkyl, halogenated C1-C10 alkyl, C1-C10 alkoxy, halogenated C1-C10 alkoxy, and halogen, and more preferably selected from the group consisting of hydrogen, C1-C6 alkyl, halogenated C1-C6 alkyl, C1-C6 alkoxy, halogenated C1-C6 alkoxy, and halogen.

[0052] In some embodiments of these sub-aspects, the diimine-metal complex is as represented by the formula IIIa:

[0053] Chemical formula IIIa

[0054] In the above chemical formula IIIa, R 1 -R 5 Each is independently selected from the group consisting of hydrogen, a halogen, a C1-C6 alkyl having or not having substituent Q, and a C1-C6 alkoxy having or not having substituent Q; R5-R 10Each is independently selected from the group consisting of hydrogen, halogen, C1-C6 alkyl, and C1-C6 alkoxy; each M is nickel; each Y is O; each X is independently a halogen; and each R 11 is a C1-C6 alkyl that independently has or does not have substituent Q.

[0055] In some embodiments of these sub-aspects, the diimine-metal complex according to the present invention is selected from the group consisting of the following:

[0056] 1) A complex represented by the chemical formula IIIa, where R 1 =R 3 =isopropyl, R 2 =R 4 =R 5 =R5- R 10 =H, R 11 =methyl, M=Ni, Y=O, X=Br;

[0057] 2) A complex represented by the chemical formula IIIa, where R 1 =R 3 =ethyl, R 2 =R 4 =R 5 =R5- R 10 =H, R 11 =methyl, M=Ni, Y=O, X=Br;

[0058] 3) A complex represented by the chemical formula IIIa, where R 1 =R 3 =methyl, R 2 =R 4 =R 5 =R5- R 10 =H, R 11 =methyl, M=Ni, Y=O, X=Br;

[0059] 4) A complex represented by the chemical formula IIIa, where R 1 - R 3 =methyl, R 4 =R 5 =R5- R 10 =H, R 11 =methyl, M=Ni, Y=O, X=Br;

[0060] 5) A complex represented by the chemical formula IIIa, where R 1 =R 3 =methyl, R 2 =Br, R 4 =R 5 =R5- R 10 =H, R 11 =methyl, M=Ni, Y=O, X=Br;

[0061] 6) A complex represented by the chemical formula IIIa, where R 1 =R 3 =Br, R 2 =R 4 =R 5 =R5- R 10 =H, R 11 =methyl, M=Ni, Y=O, X=Br;

[0062] 7) A complex represented by the chemical formula IIIa, where R 1 =R 3 =Cl, R 2 =R 4 =R 5 =R5- R 10 =H, R 11 =methyl, M=Ni, Y=O, X=Br;

[0063] 8) A complex represented by the chemical formula IIIa, where R 1 =R 3 =F, R 2 =R 4 =R 5 =R5- R 10 =H, R 11 =methyl, M=Ni, Y=O, X=Br;

[0064] 9) A complex represented by the chemical formula IIIa, where R 1 =R 3 =isopropyl, R 2 =R 4 =R 5 =R5- R 10 =H, R 11 =ethyl, M=Ni, Y=O, X=Br;

[0065] 10) A complex represented by the chemical formula IIIa, where R 1 =R3 =ethyl, R 2 =R 4 =R 5 =R5- R 10 =H, R 11 =ethyl, M=Ni, Y=O, X=Br;

[0066] 11) A complex represented by the chemical formula IIIa, where R 1 =R 3 =methyl, R 2 =R 4 =R 5 =R5- R 10 =H, R 11 =ethyl, M=Ni, Y=O, X=Br;

[0067] 12) A complex represented by the chemical formula IIIa, where R 1 - R 3 =methyl, R 4 =R 5 =R5- R 10 =H, R 11 =ethyl, M=Ni, Y=O, X=Br;

[0068] 13) A complex represented by the chemical formula IIIa, where R 1 =R 3 =methyl, R 2 =Br, R 4 =R 5 =R5- R 10 =H, R 11 =ethyl, M=Ni, Y=O, X=Br;

[0069] 14) A complex represented by the chemical formula IIIa, where R 1 =R 3 =Br, R 2 =R 4 =R 5 =R5- R 10 =H, R 11 =ethyl, M=Ni, Y=O, X=Br;

[0070] 15) A complex represented by the chemical formula IIIa, where R 1 =R 3 =Cl, R 2 =R 4 =R 5 =R5- R10 =H, R 11 =ethyl, M=Ni, Y=O, X=Br;

[0071] 16) A complex represented by the chemical formula IIIa, where R 1 =R 3 =F, R 2 =R 4 =R 5 =R5- R 10 =H, R 11 =ethyl, M=Ni, Y=O, X=Br;

[0072] 17) A complex represented by the chemical formula IIIa, where R 1 =R 3 =isopropyl, R 2 =R 4 =R 5 =R5- R 10 =H, R 11 =Isobutyl, M=Ni, Y=O, X=Br;

[0073] 18) A complex represented by the chemical formula IIIa, where R 1 =R 3 =ethyl, R 2 =R 4 =R 5 =R5- R 10 =H, R 11 =Isobutyl, M=Ni, Y=O, X=Br;

[0074] 19) A complex represented by the chemical formula IIIa, where R 1 =R 3 =methyl, R 2 =R 4 =R 5 =R5- R 10 =H, R 11 =Isobutyl, M=Ni, Y=O, X=Br;

[0075] 20) A complex represented by the chemical formula IIIa, where R 1 - R 3 =methyl, R 4 =R 5 =R5- R 10 =H, R 11 =Isobutyl, M=Ni, Y=O, X=Br;

[0076] 21) A complex represented by the chemical formula IIIa, where R 1 =R 3 =methyl, R 2 =Br, R 4 =R 5 =R5- R 10 =H, R 11 =Isobutyl, M=Ni, Y=O, X=Br;

[0077] 22) A complex represented by the chemical formula IIIa, where R 1 =R 3 =Br, R 2 =R 4 =R 5 =R5- R 10 =H, R 11 =Isobutyl, M=Ni, Y=O, X=Br;

[0078] 23) A complex represented by the chemical formula IIIa, where R 1 =R 3 =Cl, R 2 =R 4 =R 5 =R5- R 10 =H, R 11 =Isobutyl, M=Ni, Y=O, X=Br;

[0079] 24) A complex represented by the chemical formula IIIa, where R 1 =R 3 =F, R 2 =R 4 =R 5 =R5- R 10 =H, R 11 =Isobutyl, M=Ni, Y=O, X=Br;

[0080] 25) A complex represented by the chemical formula IIIa, where R 1 =R 3 =isopropyl, R 2 =R 4 =R 5 =R5=R6=R9=R 10 =H, R7=R8=methyl, R 11 =ethyl, M=Ni, Y=O, X=Br;

[0081] 26) A complex represented by the chemical formula IIIa, where R 1 =R 3 =ethyl, R 2 =R 4 =R 5 =R5=R6=R9=R 10 =H, R7=R8=methyl, R 11 =ethyl, M=Ni, Y=O, X=Br;

[0082] 27) A complex represented by the chemical formula IIIa, where R 1 =R 3 =methyl, R 2 =R 4 =R 5 =R5=R6=R9=R 10 =H, R7=R8=methyl, R 11 =ethyl, M=Ni, Y=O, X=Br;

[0083] 28) A complex represented by the chemical formula IIIa, where R 1 - R 3 =methyl, R 4 =R 5 =R5=R6=R9=R 10 =H, R7=R8=methyl, R 11 =ethyl, M=Ni, Y=O, X=Br;

[0084] 29) A complex represented by the chemical formula IIIa, where R 1 =R 3 =methyl, R 2 =Br, R 4 =R 5 =R5=R6=R9=R 10 =H, R7=R8=methyl, R 11 =ethyl, M=Ni, Y=O, X=Br;

[0085] 30) A complex represented by the chemical formula IIIa, where R 1 =R 3 =Br, R 2 =R 4 =R 5 =R5=R6=R9=R 10 =H, R7=R8=methyl, R 11 =ethyl, M=Ni, Y=O, X=Br;

[0086] 31) A complex represented by the chemical formula IIIa, where R 1 =R 3 =Cl, R 2 =R 4 =R 5 =R5=R6=R9=R 10 =H, R7=R8=methyl, R 11 =ethyl, M=Ni, Y=O, X=Br; and

[0087] 32) A complex represented by the chemical formula IIIa, where R 1 =R 3 =F, R 2 =R 4 =R 5 =R5=R6=R9=R 10 =H, R7=R8=methyl, R 11 =ethyl, M=Ni, Y=O, X=Br.

[0088] In a lower aspect, the dimine-metal complex according to the present invention is represented by the chemical formula Ib:

[0089] Chemical formula Ib

[0090] In the above chemical formula Ib, R1 and R2 are each independently C1-C30 hydrocarbyl having or not having substituent Q; R5-R8 are each independently selected from the group consisting of hydrogen, halogen, hydroxyl, and C1-C20 hydrocarbyl having or not having substituent Q, and R5-R8 are optionally connected to form a ring or ring system; and each R 12 is independently a C1-C20 hydrocarbyl with or without substituent Q; each Y is independently a Group VIA nonmetal atom; each M is independently a Group VIII metal; and each X is independently selected from the group consisting of a halogen, a C1-C10 hydrocarbyl with or without substituent Q, and a C1-C10 hydrocarbyloxy with or without substituent Q.

[0091] In some embodiments of these sub-aspects, R1 and R2 are independently selected from the group consisting of C1-C20 alkyls having or not having substituent Q and C6-C20 aryls having or not having substituent Q. Preferably, R1 and / or R2 are groups represented by the formula A:

[0092] Chemical formula A

[0093] In the above chemical formula A, R 1 -R 5 Each is independently selected from the group consisting of hydrogen, halogen, hydroxyl, C1-C20 alkyl having or not having substituent Q, C2-C20 alkenyl having or not having substituent Q, C2-C20 alkynyl having or not having substituent Q, C1-C20 alkoxy having or not having substituent Q, C2-C20 alkenoxy having or not having substituent Q, C2-C20 alkynoxy having or not having substituent Q, C6-C20 aryl having or not having substituent Q, C6-C20 aryloxy having or not having substituent Q, C7-C20 aralkyl having or not having substituent Q, C7-C20 aralkoxy having or not having substituent Q, C7-C20 alkaryl having or not having substituent Q, and C7-C20 alkaryloxy having or not having substituent Q, and R 1 -R 5 are optionally connected to form a ring or ring system. Preferably, R 1 -R 5Each independently hydrogen, halogen, hydroxy, C1-C10 alkyl having or not having substituent Q, C2-C10 alkenyl having or not having substituent Q, C2-C10 alkynyl having or not having substituent Q, C3-C10 cycloalkyl having or not having substituent Q, C1-C10 alkoxy having or not having substituent Q, C2-C10 alkenoxy having or not having substituent Q, C2-C10 alkynoxy having or not having substituent Q, C3-C10 cycloalkoxy having or not having substituent Q, C6-C15 aryl having or not having substituent Q, C6-C15 aryloxy having or not having substituent Q, C7-C15 aralkyl having or not having substituent Q, C7-C15 aralkoxy having or not having substituent Q, and having or not having substituent Q It is selected from the group consisting of C7-C15 alkalil and C7-C15 alkaliloxy having or not having substituent Q.

[0094] In some embodiments of these sub-aspects, each M is independently selected from the group consisting of nickel and palladium.

[0095] In some implementations of these sub-aspects, each Y is independently selected from the group consisting of O and S.

[0096] In some embodiments of these sub-aspects, each X is independently selected from the group consisting of a halogen, a C1-C10 alkyl having or not having substituent Q, and a C1-C10 alkoxy having or not having substituent Q, and preferably selected from the group consisting of a halogen, a C1-C6 alkyl having or not having substituent Q, and a C1-C6 alkoxy having or not having substituent Q.

[0097] In some implementations of these sub-aspects, each R 12is a C1-C20 alkyl having or not having a substituent Q independently, preferably a C1-C10 alkyl having or not having a substituent Q, more preferably a C1-C6 alkyl having or not having a substituent Q.

[0098] In some embodiments of these sub-aspects, the substituent Q is selected from the group consisting of halogen, hydroxy, C1-C10 alkyl, halogenated C1-C10 alkyl, C1-C10 alkoxy, and halogenated C1-C10 alkoxy, and preferably selected from the group consisting of halogen, hydroxy, C1-C6 alkyl, halogenated C1-C6 alkyl, C1-C6 alkoxy, and halogenated C1-C6 alkoxy. Preferably, the C1-C6 alkyl is selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, isopentyl, n-hexyl, isohexyl, and 3,3-dimethylbutyl. Preferably, the C1-C6 alkoxy is selected from the group consisting of methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, iso-butoxy, n-pentoxy, iso-pentoxy, n-hexoxy, iso-hexoxy, and 3,3-dimethylbutoxy.

[0099] In some embodiments of these sub-aspects, the diimine-metal complex is as represented by the formula IIIb:

[0100] Chemical formula IIIb

[0101] In the above chemical formula IIIb, R 1 -R 11Each is independently selected from the group consisting of hydrogen, halogen, hydroxy, C1-C20 alkyl having or not having substituent Q, C2-C20 alkenyl having or not having substituent Q, C2-C20 alkynyl having or not having substituent Q, C1-C20 alkoxy having or not having substituent Q, C2-C20 alkenoxy having or not having substituent Q, C2-C20 alkynoxy having or not having substituent Q, C6-C20 aryl having or not having substituent Q, C6-C20 aryloxy having or not having substituent Q, C7-C20 aralkyl having or not having substituent Q, C7-C20 aralkoxy having or not having substituent Q, C7-C20 alkaryl having or not having substituent Q, and C7-C20 alkaryloxy having or not having substituent Q.

[0102] M, X, Y, and R 12 is as defined above for the chemical formula Ib.

[0103] In some implementations of these sub-aspects, R 1 -R 11Each is independently hydrogen, halogen, hydroxyl, C1-C10 alkyl having or not having substituent Q, C2-C10 alkenyl having or not having substituent Q, C2-C10 alkynyl having or not having substituent Q, C3-C10 cycloalkyl having or not having substituent Q, C1-C10 alkoxy having or not having substituent Q, C2-C10 alkenoxy having or not having substituent Q, C2-C10 alkynoxy having or not having substituent Q, C3-C10 cycloalkoxy having or not having substituent Q, C6-C15 aryl having or not having substituent Q, C6-C15 aryloxy having or not having substituent Q, C7-C15 aralkyl having or not having substituent Q, C7-C15 aralkoxy having or not having substituent Q, and having or not having substituent Q It is selected from the group consisting of C7-C15 alkalil and C7-C15 alkaliloxy having or not having substituent Q. Preferably, R1-R 11 Each is independently selected from the group consisting of hydrogen, C1-C10 alkyl, halogenated C1-C10 alkyl, C1-C10 alkoxy, halogenated C1-C10 alkoxy, and halogen, and more preferably selected from the group consisting of hydrogen, C1-C6 alkyl, halogenated C1-C6 alkyl, C1-C6 alkoxy, halogenated C1-C6 alkoxy, and halogen.

[0104] In some embodiments of these sub-aspects, the diimine-metal complex according to the present invention is selected from the group consisting of the following:

[0105] 1) A diimine-metal complex represented by the chemical formula IIIb, where R 1 =R 3 =methyl, R 2 =R 4 -R 7 =R 10 =H, R 8 =R 9 =R 11 =R 12 =methyl, M=Ni, Y=O, X=Br;

[0106] 2) A diimine-metal complex represented by the chemical formula IIIb, where R 1 =R 3 =ethyl, R 2 =R 4 -R 7 =R 10 =H, R 8 =R 9 =R 11 =R 12 =methyl, M=Ni, Y=O, X=Br;

[0107] 3) A dimine-metal complex represented by the chemical formula IIIb, where R 1 =R 3 =isopropyl, R 2 =R 4 -R 7 =R 10 =H, R 8 =R 9 =R 11 =R 12 =methyl, M=Ni, Y=O, X=Br;

[0108] 4) A diimine-metal complex represented by the chemical formula IIIb, where R 1 -R 3 =methyl, R 4 -R 7 =R 10 =H, R 8 =R 9 =R 11 =R 12 =methyl, M=Ni, Y=O, X=Br;

[0109] 5) A diimine-metal complex represented by the chemical formula IIIb, where R 1 =R 3 =methyl, R 2 =Br, R 4 -R 7 =R 10 =H, R 8 =R 9 =R 11 =R 12 =methyl, M=Ni, Y=O, X=Br;

[0110] 6) A diimine-metal complex represented by the chemical formula IIIb, where R1 =R 3 =F, R 2 =R 4 -R 7 =R 10 =H, R 8 =R 9 =R 11 =R 12 =methyl, M=Ni, Y=O, X=Br;

[0111] 7) A diimine-metal complex represented by the chemical formula IIIb, where R 1 =R 3 =Cl, R 2 =R 4 -R 7 =R 10 =H, R 8 =R 9 =R 11 =R 12 =methyl, M=Ni, Y=O, X=Br;

[0112] 8) A diimine-metal complex represented by the chemical formula IIIb, where R 1 =R 3 =Br, R 2 =R 4 -R 7 =R 10 =H, R 8 =R 9 =R 11 =R 12 =methyl, M=Ni, Y=O, X=Br;

[0113] 9) A dimine-metal complex represented by the chemical formula IIIb, where R 1 =R 3 =methyl, R 2 =R 4 -R 7 =R 10 =H, R 8 =R 9 =R 11 =methyl, R 12 =ethyl, M=Ni, Y=O, X=Br;

[0114] 10) A diimine-metal complex represented by the chemical formula IIIb, where R 1 =R 3 =ethyl, R 2 =R4 -R 7 =R 10 =H, R 8 =R 9 =R 11 =methyl, R 12 =ethyl, M=Ni, Y=O, X=Br;

[0115] 11) A diimine-metal complex represented by the chemical formula IIIb, where R 1 =R 3 =isopropyl, R 2 =R 4 -R 7 =R 10 =H, R 8 =R 9 =R 11 =methyl, R 12 =ethyl, M=Ni, Y=O, X=Br;

[0116] 12) A diimine-metal complex represented by the chemical formula IIIb, where R 1 -R 3 =methyl, R 4 -R 7 =R 10 =H, R 8 =R 9 =R 11 =methyl, R 12 =ethyl, M=Ni, Y=O, X=Br;

[0117] 13) A diimine-metal complex represented by the chemical formula IIIb, where R 1 =R 3 =methyl, R 2 =Br, R 4 -R 7 =R 10 =H, R 8 =R 9 =R 11 =methyl, R 12 =ethyl, M=Ni, Y=O, X=Br;

[0118] 14) A diimine-metal complex represented by the chemical formula IIIb, where R 1 =R 3 =F, R 2 =R 4 -R 7 =R 10 =H, R8 =R 9 =R 11 =methyl, R 12 =ethyl, M=Ni, Y=O, X=Br;

[0119] 15) A diimine-metal complex represented by the chemical formula IIIb, where R 1 =R 3 =Cl, R 2 =R 4 -R 7 =R 10 =H, R 8 =R 9 =R 11 =methyl, R 12 =ethyl, M=Ni, Y=O, X=Br;

[0120] 16) A diimine-metal complex represented by the chemical formula IIIb, where R 1 =R 3 =Br, R 2 =R 4 -R 7 =R 10 =H, R 8 =R 9 =R 11 =methyl, R 12 =ethyl, M=Ni, Y=O, X=Br;

[0121] 17) A dimine-metal complex represented by the chemical formula IIIb, where R 1 =R 3 =methyl, R 2 =R 4 -R 7 =R 10 =H, R 8 =R 9 =R 11 =methyl, R 12 =Isobutyl, M=Ni, Y=O, X=Br;

[0122] 18) A diimine-metal complex represented by the chemical formula IIIb, where R 1 =R 3 =ethyl, R 2 =R 4 -R 7 =R 10 =H, R 8 =R 9 =R11 =methyl, R 12 =Isobutyl, M=Ni, Y=O, X=Br;

[0123] 19) A dimine-metal complex represented by the chemical formula IIIb, where R 1 =R 3 =isopropyl, R 2 =R 4 -R 7 =R 10 =H, R 8 =R 9 =R 11 =methyl, R 12 =Isobutyl, M=Ni, Y=O, X=Br;

[0124] 20) A diimine-metal complex represented by the chemical formula IIIb, where R 1 -R 3 =methyl, R 4 -R 7 =R 10 =H, R 8 =R 9 =R 11 =methyl, R 12 =Isobutyl, M=Ni, Y=O, X=Br;

[0125] 21) A diimine-metal complex represented by the chemical formula IIIb, where R 1 =R 3 =methyl, R 2 =Br, R 4 -R 7 =R 10 =H, R 8 =R 9 =R 11 =methyl, R 12 =Isobutyl, M=Ni, Y=O, X=Br;

[0126] 22) A diimine-metal complex represented by the chemical formula IIIb, where R 1 =R 3 =F, R 2 =R 4 -R 7 =R 10 =H, R 8 =R 9 =R 11 =methyl, R 12=Isobutyl, M=Ni, Y=O, X=Br;

[0127] 23) A diimine-metal complex represented by the chemical formula IIIb, where R 1 =R 3 =Cl, R 2 =R 4 -R 7 =R 10 =H, R 8 =R 9 =R 11 =methyl, R 12 =Isobutyl, M=Ni, Y=O, X=Br;

[0128] 24) A diimine-metal complex represented by the chemical formula IIIb, where R 1 =R 3 =Br, R 2 =R 4 -R 7 =R 10 =H, R 8 =R 9 =R 11 =methyl, R 12 =Isobutyl, M=Ni, Y=O, X=Br;

[0129] 25) A diimine-metal complex represented by the chemical formula IIIb, where R 1 =R 3 =methyl, R 2 =R 4 -R 7 =R 10 =H, R 8 =R 9 =methyl, R 11 =bromomethyl, R 12 =ethyl, M=Ni, Y=O, X=Br;

[0130] 26) A diimine-metal complex represented by the chemical formula IIIb, where R 1 =R 3 =ethyl, R 2 =R 4 -R 7 =R 10 =H, R 8 =R 9 =methyl, R 11 =bromomethyl, R 12=ethyl, M=Ni, Y=O, X=Br;

[0131] 27) A diimine-metal complex represented by the chemical formula IIIb, where R 1 =R 3 =isopropyl, R 2 =R 4 -R 7 =R 10 =H, R 8 =R 9 =methyl, R 11 =bromomethyl, R 12 =ethyl, M=Ni, Y=O, X=Br;

[0132] 28) A diimine-metal complex represented by the chemical formula IIIb, where R 1 -R 3 =methyl, R 4 -R 7 =R 10 =H, R 8 =R 9 =methyl, R 11 =bromomethyl, R 12 =ethyl, M=Ni, Y=O, X=Br;

[0133] 29) A dimine-metal complex represented by the chemical formula IIIb, where R 1 =R 3 =methyl, R 2 =Br, R 4 -R 7 =R 10 =H, R 8 =R 9 =methyl, R 11 =bromomethyl, R 12 =ethyl, M=Ni, Y=O, X=Br;

[0134] 30) A diimine-metal complex represented by the chemical formula IIIb, where R 1 =R 3 =F, R 2 =R 4 -R 7 =R 10 =H, R 8 =R 9 =methyl, R 11 =bromomethyl, R 12=ethyl, M=Ni, Y=O, X=Br;

[0135] 31) A diimine-metal complex represented by the chemical formula IIIb, where R 1 =R 3 =Cl, R 2 =R 4 -R 7 =R 10 =H, R 8 =R 9 =methyl, R 11 =bromomethyl, R 12 =ethyl, M=Ni, Y=O, X=Br;

[0136] 32) A diimine-metal complex represented by the chemical formula IIIb, where R 1 =R 3 =Br, R 2 =R 4 -R 7 =R 10 =H, R 8 =R 9 =methyl, R 11 =bromomethyl, R 12 =ethyl, M=Ni, Y=O, X=Br.

[0137] In another sub-aspect, the diimine-metal complex according to the present invention is represented by the chemical formula Ic:

[0138] Chemical formula Ic

[0139] In the above chemical formula Ic, R 21 -R 24 Each is independently selected from the group consisting of hydrogen, halogen, hydroxyl, C1-C20 hydrocarbyl having or not having substituent Q, and C1-C20 hydrocarbyloxy having or not having substituent Q, and R 21 -R 24 are optionally connected to form a ring or ring system; R1, R2, R 11 , Y, M and X are as defined above for chemical formula I.

[0140] In some embodiments of these sub-aspects, R1 and R2 are independently selected from the group consisting of C1-C20 alkyls having or not having substituent Q and C6-C20 aryls having or not having substituent Q. Preferably, R1 and / or R2 are groups represented by the formula A:

[0141] Chemical formula A

[0142] In the above chemical formula A, R 1 -R 5 Each is independently selected from the group consisting of hydrogen, halogen, hydroxyl, C1-C20 alkyl having or not having substituent Q, C2-C20 alkenyl having or not having substituent Q, C2-C20 alkynyl having or not having substituent Q, C1-C20 alkoxy having or not having substituent Q, C2-C20 alkenoxy having or not having substituent Q, C2-C20 alkynoxy having or not having substituent Q, C6-C20 aryl having or not having substituent Q, C6-C20 aryloxy having or not having substituent Q, C7-C20 aralkyl having or not having substituent Q, C7-C20 aralkoxy having or not having substituent Q, C7-C20 alkaryl having or not having substituent Q, and C7-C20 alkaryloxy having or not having substituent Q, and R 1 -R 5 are optionally connected to form a ring or ring system. Preferably, R 1 -R 5Each independently hydrogen, halogen, hydroxy, C1-C10 alkyl having or not having substituent Q, C2-C10 alkenyl having or not having substituent Q, C2-C10 alkynyl having or not having substituent Q, C3-C10 cycloalkyl having or not having substituent Q, C1-C10 alkoxy having or not having substituent Q, C2-C10 alkenoxy having or not having substituent Q, C2-C10 alkynoxy having or not having substituent Q, C3-C10 cycloalkoxy having or not having substituent Q, C6-C15 aryl having or not having substituent Q, C6-C15 aryloxy having or not having substituent Q, C7-C15 aralkyl having or not having substituent Q, C7-C15 aralkoxy having or not having substituent Q, and having or not having substituent Q It is selected from the group consisting of C7-C15 alkalil and C7-C15 alkaliloxy having or not having substituent Q.

[0143] In some embodiments of these sub-aspects, each M is independently selected from the group consisting of nickel and palladium.

[0144] In some implementations of these sub-aspects, each Y is independently selected from the group consisting of O and S.

[0145] In some embodiments of these sub-aspects, each X is independently selected from the group consisting of a halogen, a C1-C10 alkyl having or not having substituent Q, and a C1-C10 alkoxy having or not having substituent Q, and preferably selected from the group consisting of a halogen, a C1-C6 alkyl having or not having substituent Q, and a C1-C6 alkoxy having or not having substituent Q.

[0146] In some implementations of these sub-aspects, each R 11is independently a C1-C20 alkyl having or not having substituent Q, preferably a C1-C10 alkyl having or not having substituent Q, more preferably a C1-C6 alkyl having or not having substituent Q.

[0147] In some embodiments of these sub-aspects, the substituent Q is selected from the group consisting of halogen, hydroxy, C1-C10 alkyl, halogenated C1-C10 alkyl, C1-C10 alkoxy, and halogenated C1-C10 alkoxy, and preferably selected from the group consisting of halogen, hydroxy, C1-C6 alkyl, halogenated C1-C6 alkyl, C1-C6 alkoxy, and halogenated C1-C6 alkoxy. Preferably, the C1-C6 alkyl is selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, isopentyl, n-hexyl, isohexyl, and 3,3-dimethylbutyl. Preferably, the C1-C6 alkoxy is selected from the group consisting of methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, iso-butoxy, n-pentoxy, iso-pentoxy, n-hexoxy, iso-hexoxy, and 3,3-dimethylbutoxy.

[0148] In some embodiments of these sub-aspects, the diimine-metal complex according to the present invention has a structure represented by the formula IIIc:

[0149] Chemical formula IIIc

[0150] In the above chemical formula IIIc, R 1 -R 10 , R 21 -R 24Each is independently selected from the group consisting of hydrogen, halogen, hydroxyl, C1-C20 alkyl having or not having substituent Q, C2-C20 alkenyl having or not having substituent Q, C2-C20 alkynyl having or not having substituent Q, C1-C20 alkoxy having or not having substituent Q, C2-C20 alkenoxy having or not having substituent Q, C2-C20 alkynoxy having or not having substituent Q, C6-C20 aryl having or not having substituent Q, C6-C20 aryloxy having or not having substituent Q, C7-C20 aralkyl having or not having substituent Q, C7-C20 aralkoxy having or not having substituent Q, C7-C20 alkaryl having or not having substituent Q, and C7-C20 alkaryloxy having or not having substituent Q, and R 1 -R 10 ... are optionally connected to form a ring or ring system, and R 21 -R 24 is optionally connected to form a ring or ring system; R 11 , Y, M and X are as defined above for the chemical formula Ic.

[0151] In some implementations of these sub-aspects, R 1 -R 11 , R 21 -R 24Each independently hydrogen, halogen, hydroxy, C1-C10 alkyl having or not having substituent Q, C2-C10 alkenyl having or not having substituent Q, C2-C10 alkynyl having or not having substituent Q, C3-C10 cycloalkyl having or not having substituent Q, C1-C10 alkoxy having or not having substituent Q, C2-C10 alkenoxy having or not having substituent Q, C2-C10 alkynoxy having or not having substituent Q, C3-C10 cycloalkoxy having or not having substituent Q, C6-C15 aryl having or not having substituent Q, C6-C15 aryloxy having or not having substituent Q, C7-C15 aralkyl having or not having substituent Q, C7-C15 aralkoxy having or not having substituent Q, and having or not having substituent Q It is selected from the group consisting of C7-C15 alkalil and C7-C15 alkaliloxy having or not having substituent Q. Preferably, R 1 -R 11 , R 21 -R 24 Each is independently selected from the group consisting of hydrogen, C1-C10 alkyl, halogenated C1-C10 alkyl, C1-C10 alkoxy, halogenated C1-C10 alkoxy, and halogen, and more preferably selected from the group consisting of hydrogen, C1-C6 alkyl, halogenated C1-C6 alkyl, C1-C6 alkoxy, halogenated C1-C6 alkoxy, and halogen.

[0152] In some embodiments of these sub-aspects, the diimine-metal complex of the present invention has a structure represented by the formula IIc:

[0153] Chemical formula IIc

[0154] In the above chemical formula IIc, R 31 -R 34 R in the chemical formula Ic 21 -R 24 It has the same meaning as, and preferably R 33 and R34 is hydrogen; R 11 , Y, M and X are as defined above for the chemical formula Ic.

[0155] In some implementations, R 31 -R 34 Each is independently selected from the group consisting of hydrogen, hydroxy, C1-C20 alkyl having or not having substituent Q, C2-C20 alkenyl having or not having substituent Q, C2-C20 alkynyl having or not having substituent Q, C1-C20 alkoxy having or not having substituent Q, C2-C20 alkenoxy having or not having substituent Q, C2-C20 alkynoxy having or not having substituent Q, C6-C20 aryl having or not having substituent Q, C6-C20 aryloxy having or not having substituent Q, C7-C20 aralkyl having or not having substituent Q, C7-C20 aralkoxy having or not having substituent Q, C7-C20 alkaryl having or not having substituent Q, C7-C20 alkaryloxy having or not having substituent Q, and halogen. Preferably, R 31 -R 34Each independently hydrogen, halogen, hydroxy, C1-C10 alkyl having or not having substituent Q, C2-C10 alkenyl having or not having substituent Q, C2-C10 alkynyl having or not having substituent Q, C3-C10 cycloalkyl having or not having substituent Q, C1-C10 alkoxy having or not having substituent Q, C2-C10 alkenoxy having or not having substituent Q, C2-C10 alkynoxy having or not having substituent Q, C3-C10 cycloalkoxy having or not having substituent Q, C6-C15 aryl having or not having substituent Q, C6-C15 aryloxy having or not having substituent Q, C7-C15 aralkyl having or not having substituent Q, C7-C15 aralkoxy having or not having substituent Q, and having or not having substituent Q It is selected from the group consisting of C7-C15 alkalil and C7-C15 alkaliloxy having or not having substituent Q. More preferably, R 31 -R 34 Each is independently selected from the group consisting of hydrogen, C1-C10 alkyl, halogenated C1-C10 alkyl, C1-C10 alkoxy, halogenated C1-C10 alkoxy, and halogen, and more preferably selected from the group consisting of hydrogen, C1-C6 alkyl, halogenated C1-C6 alkyl, C1-C6 alkoxy, halogenated C1-C6 alkoxy, and halogen.

[0156] In some embodiments of these sub-aspects, the diimine-metal complex of the present invention is selected from the group consisting of the following:

[0157] 1) A complex represented by the chemical formula IIIc, where R 1 =R 3 =R 4 =R 6 =isopropyl, R 2 =R 5 =R 7 -R 10 =R 21 =R 22 =R 23 =R24 =H, R 11 =ethyl, M=Ni, Y=O, X=Br;

[0158] 2) A complex represented by the chemical formula IIIc, where R 1 =R 3 =R 4 =R 6 =ethyl, R 2 =R 5 =R 7 -R 10 =R 21 =R 22 =R 23 =R 24 =H, R 11 =ethyl, M=Ni, Y=O, X=Br;

[0159] 3) A complex represented by the chemical formula IIIc, where R 1 =R 3 =R 4 =R 6 =methyl, R 2 =R 5 =R 7 -R 10 =R 21 =R 22 =R 23 =R 24 =H, R 11 =ethyl, M=Ni, Y=O, X=Br;

[0160] 4) A complex represented by the chemical formula IIIc, where R 1 -R 6 =methyl, R 7 -R 10 =R 21 =R 22 =R 23 =R 24 =H, R 11 =ethyl, M=Ni, Y=O, X=Br;

[0161] 5) A complex represented by the chemical formula IIIc, where R 1 =R 3 =R 4 =R 6 =Br, R 2 =R 5 =R 7 -R 10 =R 21=R 22 =R 23 =R 24 =H, R 11 =ethyl, M=Ni, Y=O, X=Br;

[0162] 6) A complex represented by the chemical formula IIIc, where R 1 =R 3 =R 4 =R 6 =Cl, R 2 =R 5 =R 7 -R 10 =R 21 =R 22 =R 23 =R 24 =H, R 11 =ethyl, M=Ni, Y=O, X=Br;

[0163] 7) A complex represented by the chemical formula IIIc, where R 1 =R 3 =R 4 =R 6 =F, R 2 =R 5 =R 7 -R 10 =R 21 =R 22 =R 23 =R 24 =H, R 11 =ethyl, M=Ni, Y=O, X=Br;

[0164] 8) A complex represented by the chemical formula IIIc, where R 1 =R 3 =R 4 =R 6 =isopropyl, R 2 =R 5 =R 7 -R 10 =R 21 =R 22 =R 23 =R 24 =H, R 11 =Isobutyl, M=Ni, Y=O, X=Br;

[0165] 9) A complex represented by the chemical formula IIIc, where R 1 =R 3 =R4 =R 6 =ethyl, R 2 =R 5 =R 7 -R 10 =R 21 =R 22 =R 23 =R 24 =H, R 11 =Isobutyl, M=Ni, Y=O, X=Br;

[0166] 10) A complex represented by the chemical formula IIIc, where R 1 =R 3 =R 4 =R 6 =methyl, R 2 =R 5 =R 7 -R 10 =R 21 =R 22 =R 23 =R 24 =H, R 11 =Isobutyl, M=Ni, Y=O, X=Br;

[0167] 11) A complex represented by the chemical formula IIIc, where R 1 -R 6 =methyl, R 7 -R 10 =R 21 =R 22 =R 23 =R 24 =H, R 11 =Isobutyl, M=Ni, Y=O, X=Br;

[0168] 12) A complex represented by the chemical formula IIIc, where R 1 =R 3 =R 4 =R 6 =Br, R 2 =R 5 =R 7 - R 10 =R 21 =R 22 =R 23 =R 24 =H, R 11 =Isobutyl, M=Ni, Y=O, X=Br;

[0169] 13) A complex represented by the chemical formula IIIc, where R 1 =R 3 =R 4 =R 6 =Cl, R 2 =R 5 =R 7 -R 10 =R 21 =R 22 =R 23 =R 24 =H, R 11 =Isobutyl, M=Ni, Y=O, X=Br;

[0170] 14) A complex represented by the chemical formula IIIc, where R 1 =R 3 =R 4 =R 6 =F, R 2 =R 5 =R 7 -R 10 =R 21 =R 22 =R 23 =R 24 =H, R 11 =Isobutyl, M=Ni, Y=O, X=Br;

[0171] 15) A complex represented by the chemical formula IIIc, where R 1 =R 3 =R 4 =R 6 =isopropyl, R 2 =R 5 =R 7 -R 10 =R 22 =H, R 21 =tert-butyl, R 23 =R 24 =H, R 11 =ethyl, M=Ni, Y=O, X=Br;

[0172] 16) A complex represented by the chemical formula IIIc, where R 1 =R 3 =R 4 =R 6 =ethyl, R 2 =R 5 =R 7 -R 10 =R22 =H, R 21 =tert-butyl, R 23 =R 24 =H, R 11 =ethyl, M=Ni, Y=O, X=Br;

[0173] 17) A complex represented by the chemical formula IIIc, where R 1 =R 3 =R 4 =R 6 =methyl, R 2 =R 5 =R 7 -R 10 =R 22 =H, R 21 =tert-butyl, R 23 =R 24 =H, R 11 =ethyl, M=Ni, Y=O, X=Br;

[0174] 18) A complex represented by the chemical formula IIIc, where R 1 -R 6 =methyl, R 7 -R 10 =R 22 =H, R 21 =tert-butyl, R 23 =R 24 =H, R 11 =ethyl, M=Ni, Y=O, X=Br;

[0175] 19) A complex represented by the chemical formula IIIc, where R 1 =R 3 =R 4 =R 6 =Br, R 2 =R 5 =R 7 -R 10 =R 22 =H, R 21 =tert-butyl, R 23 =R 24 =H, R 11 =ethyl, M=Ni, Y=O, X=Br;

[0176] 20) A complex represented by the chemical formula IIIc, where R 1 =R 3 =R4 =R 6 =Cl, R 2 =R 5 =R 7 -R 10 =R 22 =H, R 21 =tert-butyl, R 23 =R 24 =H, R 11 =ethyl, M=Ni, Y=O, X=Br;

[0177] 21) A complex represented by the chemical formula IIIc, where R 1 =R 3 =R 4 =R 6 =F, R 2 =R 5 =R 7 -R 10 =R 22 =H, R 21 =tert-butyl, R 23 =R 24 =H, R 11 =ethyl, M=Ni, Y=O, X=Br;

[0178] 22) A complex represented by the chemical formula IIIc, where R 1 =R 3 =R 4 =R 6 =isopropyl, R 2 =R 5 =R 7 -R 10 =R 22 =H, R 21 =tert-butyl, R 23 =R 24 =H, R 11 =Isobutyl, M=Ni, Y=O, X=Br;

[0179] 23) A complex represented by the chemical formula IIIc, where R 1 =R 3 =R 4 =R 6 =ethyl, R 2 =R 5 =R 7 -R 10 =R 22 =H, R 21 =tert-butyl, R23 =R 24 =H, R 11 =Isobutyl, M=Ni, Y=O, X=Br;

[0180] 24) A complex represented by the chemical formula IIIc, where R 1 =R 3 =R 4 =R 6 =methyl, R 2 =R 5 =R 7 -R 10 =R 22 =H, R 21 =tert-butyl, R 23 =R 24 =H, R 11 =Isobutyl, M=Ni, Y=O, X=Br;

[0181] 25) A complex represented by the chemical formula IIIc, where R 1 -R 6 =methyl, R 7 -R 10 =R 22 =H, R 21 =tert-butyl, R 23 =R 24 =H, R 11 =Isobutyl, M=Ni, Y=O, X=Br;

[0182] 26) A complex represented by the chemical formula IIIc, where R 1 =R 3 =R 4 =R 6 =Br, R 2 =R 5 =R 7 -R 10 =R 22 =H, R 21 =tert-butyl, R 23 =R 24 =H, R 11 =Isobutyl, M=Ni, Y=O, X=Br;

[0183] 27) A complex represented by the chemical formula IIIc, where R 1 =R 3 =R 4 =R 6 =Cl, R2 =R 5 =R 7 -R 10 =R 22 =H, R 21 =tert-butyl, R 23 =R 24 =H, R 11 =Isobutyl, M=Ni, Y=O, X=Br;

[0184] 28) A complex represented by the chemical formula IIIc, where R 1 =R 3 =R 4 =R 6 =F, R 2 =R 5 =R 7 -R 10 =R 22 =H, R 21 =tert-butyl, R 23 =R 24 =H, R 11 =Isobutyl, M=Ni, Y=O, X=Br;

[0185] (IIIc')

[0186] 29) A complex represented by the chemical formula (IIIc'), where R 1 =R 3 =R 4 =R 6 =isopropyl, R 2 =R 5 =R 7 -R 10 =R 31 =R 32 =H, R 11 =ethyl, M=Ni, Y=O, X=Br;

[0187] 30) A complex represented by the chemical formula (IIIc'), where R 1 =R 3 =R 4 =R 6 =ethyl, R 2 =R 5 =R 7 -R 10 =R 31 =R 32 =H, R 11=ethyl, M=Ni, Y=O, X=Br;

[0188] 31) A complex represented by the chemical formula (IIIc'), where R 1 =R 3 =R 4 =R 6 =methyl, R 2 =R 5 =R 7 -R 10 =R 31 =R 32 =H, R 11 =ethyl, M=Ni, Y=O, X=Br;

[0189] 32) A complex represented by the chemical formula (IIIc'), where R 1 -R 6 =methyl, R 7 -R 10 =R 31 =R 32 =H, R 11 =ethyl, M=Ni, Y=O, X=Br;

[0190] 33) A complex represented by the chemical formula (IIIc'), where R 1 =R 3 =R 4 =R 6 =Br, R 2 =R 5 =R 7 -R 10 =R 31 =R 32 =H, R 11 =ethyl, M=Ni, Y=O, X=Br;

[0191] 34) A complex represented by the chemical formula (IIIc'), where R 1 =R 3 =R 4 =R 6 =Cl, R 2 =R 5 =R 7 -R 10 =R 31 =R 32 =H, R 11 =ethyl, M=Ni, Y=O, X=Br;

[0192] 35) A complex represented by the chemical formula (IIIc'), where R 1 =R 3 =R 4 =R 6 =F, R 2 =R 5 =R 7 -R 10 =R 31 =R 32 =H, R 11 =ethyl, M=Ni, Y=O, X=Br;

[0193] 36) A complex represented by the chemical formula (IIIc'), where R 1 =R 3 =R 4 =R 6 =isopropyl, R 2 =R 5 =R 7 -R 10 =R 31 =R 32 =H, R 11 =Isobutyl, M=Ni, Y=O, X=Br;

[0194] 37) A complex represented by the chemical formula (IIIc'), where R 1 =R 3 =R 4 =R 6 =ethyl, R 2 =R 5 =R 7 -R 10 =R 31 =R 32 =H, R 11 =Isobutyl, M=Ni, Y=O, X=Br;

[0195] 38) A complex represented by the chemical formula (IIIc'), where R 1 =R 3 =R 4 =R 6 =methyl, R 2 =R 5 =R 7 -R 10 =R 31 =R 32 =H, R 11 =Isobutyl, M=Ni, Y=O, X=Br;

[0196] 39) A complex represented by the chemical formula (IIIc'), where R 1 -R 6 =methyl, R 7 -R 10 =R 31 =R 32 =H, R 11 =Isobutyl, M=Ni, Y=O, X=Br;

[0197] 40) A complex represented by the chemical formula (IIIc'), where R 1 =R 3 =R 4 =R 6 =Br, R 2 =R 5 =R 7 -R 10 =R 31 =R 32 =H, R 11 =Isobutyl, M=Ni, Y=O, X=Br;

[0198] 41) A complex represented by the chemical formula (IIIc'), where R 1 =R 3 =R 4 =R 6 =Cl, R 2 =R 5 =R 7 -R 10 =R 31 =R 32 =H, R 11 =Isobutyl, M=Ni, Y=O, X=Br;

[0199] 42) A complex represented by the chemical formula (IIIc'), where R 1 =R 3 =R 4 =R 6 =F, R 2 =R 5 =R 7 -R 10 =R 31 =R 32 =H, R 11 =Isobutyl, M=Ni, Y=O, X=Br;

[0200] 43) A complex represented by the chemical formula (IIIc'), where R 1 =R 3 =R4 =R 6 =isopropyl, R 2 =R 5 =R 7 -R 10 =HR 31 =R 32 =R 11 =ethyl, M=Ni, Y=O, X=Br;

[0201] 44) A complex represented by the chemical formula (IIIc'), where R 1 =R 3 =R 4 =R 6 =ethyl, R 2 =R 5 =R 7 -R 10 =H, R 31 =R 32 =R 11 =ethyl, M=Ni, Y=O, X=Br;

[0202] 45) A complex represented by the chemical formula (IIIc'), where R 1 =R 3 =R 4 =R 6 =methyl, R 2 =R 5 =R 7 -R 10 =H, R 31 =R 32 =R 11 =ethyl, M=Ni, Y=O, X=Br;

[0203] 46) A complex represented by the chemical formula (IIIc'), where R 1 -R 6 =methyl, R 7 -R 10 =H, R 31 =R 32 =R 11 =ethyl, M=Ni, Y=O, X=Br;

[0204] 47) A complex represented by the chemical formula (IIIc'), where R 1 =R 3 =R 4 =R 6 =Br, R 2 =R 5 =R7 -R 10 =H, R 31 =R 32 =R 11 =ethyl, M=Ni, Y=O, X=Br;

[0205] 48) A complex represented by the chemical formula (IIIc'), where R 1 =R 3 =R 4 =R 6 =Cl, R 2 =R 5 =R 7 -R 10 =H, R 31 =R 32 =R 11 =ethyl, M=Ni, Y=O, X=Br;

[0206] 49) A complex represented by the chemical formula (IIIc'), where R 1 =R 3 =R 4 =R 6 =F, R 2 =R 5 =R 7 -R 10 =H, R 31 =R 32 =R 11 =ethyl, M=Ni, Y=O, X=Br;

[0207] 50) A complex represented by the chemical formula (IIIc'), where R 1 =R 3 =R 4 =R 6 =isopropyl, R 2 =R 5 =R 7 -R 10 =H, R 31 =R 32 =R 11 =ethyl, M=Ni, Y=O, X=Br;

[0208] 51) A complex represented by the chemical formula (IIIc'), where R 1 =R 3 =R 4 =R 6 =ethyl, R 2 =R 5 =R7 -R 10 =H, R 31 =R 32 =ethyl, R 11 =Isobutyl, M=Ni, Y=O, X=Br;

[0209] 52) A complex represented by the chemical formula (IIIc'), where R 1 =R 3 =R 4 =R 6 =methyl, R 2 =R 5 =R 7 -R 10 =H, R 31 =R 32 =ethyl, R 11 =Isobutyl, M=Ni, Y=O, X=Br;

[0210] 53) A complex represented by the chemical formula (IIIc'), where R 1 -R 6 =methyl, R 7 -R 10 =H, R 31 =R 32 =ethyl, R 11 =Isobutyl, M=Ni, Y=O, X=Br;

[0211] 54) A complex represented by the chemical formula (IIIc'), where R 1 =R 3 =R 4 =R 6 =Br, R 2 =R 5 =R 7 -R 10 =H, R 31 =R 32 =ethyl, R 11 =Isobutyl, M=Ni, Y=O, X=Br;

[0212] 55) A complex represented by the chemical formula (IIIc'), where R 1 =R 3 =R 4 =R 6 =Cl, R 2 =R 5 =R 7 -R 10 =H, R 31=R 32 =ethyl, R 11 =Isobutyl, M=Ni, Y=O, X=Br;

[0213] 56) A complex represented by the chemical formula (IIIc'), where R 1 =R 3 =R 4 =R 6 =F, R 2 =R 5 =R 7 -R 10 =H, R 31 =R 32 =ethyl, R 11 =Isobutyl, M=Ni, Y=O, X=Br.

[0214] In a second aspect, the present invention provides a method for preparing a diine-metal complex as described above, wherein the method comprises step 1) a diine compound represented by Formula IV, MX n and R 11 The method includes the step of reacting with YH to form a dimine-metal complex represented by the chemical formula I, and

[0215]

[0216] Chemical Formula IV Chemical Formula I

[0217] In Chemical Formula IV, R1, R2, R3, and R4 have the same definitions as in Chemical Formula I;

[0218] MX n In this, M and X have the same definitions as in Formula I, and n is the number of X satisfying the valence state of M, e.g., 1, 2, or 3;

[0219] R 11 Y and R in YH 11 It has the same definition as in Formula I of Article 1.

[0220] According to some embodiments of the present invention, the reaction of step 1) is carried out in an organic solvent, the organic solvent is preferably a halogenated alkane, and more preferably, the organic solvent is one or more selected from dichloromethane, trichloromethane, and 1,2-dichloroethane. According to some embodiments of the present invention, the reaction of step 1) is carried out at a temperature of 15-40 °C.

[0221] In some embodiments of the present invention, MX n It includes nickel halides, such as nickel bromide and nickel chloride, and 1,2-dimethoxyethane nickel halides, such as 1,2-dimethoxyethane nickel bromide and 1,2-dimethoxyethane nickel chloride.

[0222] In a third aspect, the present invention provides a use of the above-described diimine-metal complex in olefin polymerization. Preferably, the olefin comprises an α-olefin containing a polar group and ethylene.

[0223] In a fourth aspect, the present invention provides a catalyst for olefin polymerization comprising the aforementioned diimine-metal complex.

[0224] According to some embodiments of the present invention, the catalyst comprises a co-catalyst selected from the group consisting of organoaluminum compounds and / or organoboron compounds; the organoaluminum compound is independently an alkylaluminoxane or formula AlR n X 1 3-n Selected from the group consisting of organoaluminum compounds (alkylaluminum or alkylaluminum halide), where R is H, C1-C 20 Hydrocarbyl or C1-C 20 Hydrocarbyloxy, preferably C1-C 20 Alkyl, C1-C 20 Alkoxy, C7-C 20 Aralkyl or C6-C 20 Ariligo; X 1 is a halogen, preferably chlorine or bromine; and 0 <n≤3이다.

[0225] According to some embodiments of the present invention, specific examples of organoaluminum compounds include, but are not limited to, trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, trioctylaluminum, diethylaluminum hydride, diisobutylaluminum hydride, diethylaluminum chloride, diisobutylaluminum chloride, ethylaluminum sesquichloride, ethylaluminum dichloride, methylaluminoxan (MAO), and modified methylaluminoxan (MMAO). Preferably, the organoaluminum compound is methylaluminoxan (MAO).

[0226] According to some embodiments of the present invention, the organoboron compound is selected from the group consisting of aromatic hydrocarbyl boron compounds and borates. The aromatic hydrocarbyl boron compound is preferably substituted or unsubstituted phenyl boron, more preferably tris(pentafluorophenyl) boron. The borate is preferably N,N-dimethylanilinium tetrakis(pentafluorophenyl) borate and / or triphenylcarbonium tetrakis(pentafluorophenyl) borate.

[0227] According to some embodiments of the present invention, when the co-catalyst is an organoaluminum compound, the molar ratio of aluminum in the co-catalyst to M in the main catalyst is (10-10 7):1, e.g. 10:1, 20:1, 50:1, 100:1, 200:1, 300:1, 500:1, 700:1, 800:1, 1,000:1, 2,000:1, 3,000:1, 5,000:1, 10,000:1, 100,000:1, 1,000,000:1, 10,000,000:1 and any value in between, preferably (10-100000):1, more preferably (100-10,000):1; When the co-catalyst is an organoboron compound, the molar ratio of boron in the co-catalyst to M in the main catalyst is (0.1-1000):1, e.g., 0.1:1, 0.2:1, 0.5:1, 1:1, 2:1, 3:1, 5:1, 8:1, 10:1, 20:1, 50:1, 100:1, 200:1, 300:1, 500:1, 700:1, 800:1, 1,000:1 and any value in between, preferably (0.1-500):1.

[0228] According to some embodiments of the present invention, the catalyst comprises one or more chain transfer agents selected from aluminum alkyl, magnesium alkyl, boron alkyl, and zinc alkyl, and the molar ratio of chain transfer agent to main catalyst M is (0.1-5,000):1.

[0229] The catalyst provided by the present invention may be used for the homopolymerization or copolymerization of olefins, in particular for the homopolymerization of ethylene or the copolymerization of ethylene with α-olefin(s) having different hydroxyl and polar functional groups and olefin(s). The α-olefin is at least one selected from propylene, butene, pentene, hexene, octene, 4-methylpentene-1, etc. The olefin having polar functional groups may be a vinyl monomer containing one or more hydroxyl groups and / or one or more carboxyl groups. The same molecule of the vinyl monomer may contain several different polar groups.

[0230] According to some embodiments of the present invention, the olefin polymerized using the catalyst of the present invention is a C2-C16 olefin. Preferably, the olefin is ethylene or an α-olefin having 3 to 16 carbon atoms.

[0231] In a fifth aspect, the present invention provides a method for polymerizing olefins comprising carrying out an olefin polymerization reaction, such as homopolymerization or copolymerization, in the presence of the diimine-metal complex described above or the catalyst described above, wherein the temperature of the polymerization reaction is in the range of -78 °C to 200 °C, preferably -20 °C to 150 °C, and the polymerization pressure is in the range of 0.01 to 10.0 MPa, preferably 0.01 to 2.0 MPa.

[0232] According to some embodiments of the present invention, the olefin comprises a C2-C16 olefin.

[0233] According to some embodiments of the present invention, the olefin comprises a C2-C16 α-olefin.

[0234] According to some embodiments of the present invention, the olefin includes ethylene.

[0235] According to some embodiments of the present invention, the olefin includes α-olefins containing polar groups and ethylene.

[0236] According to some embodiments of the present invention, the polymerization temperature is in the range of -78 ℃ to 200 ℃, preferably -20 ℃ to 150 ℃.

[0237] According to some embodiments of the present invention, the polymerization pressure is in the range of 0.01 to 10.0 MPa, preferably 0.01 to 2.0 MPa.

[0238] According to some embodiments of the present invention, polymerization is carried out using olefin monomers in a solvent, and the solvent for polymerization is one or more selected from alkanes, aromatic hydrocarbons, and halogenated hydrocarbons.

[0239] According to some specific embodiments of the present invention, the solvent for polymerization is one or more selected from hexane, pentane, heptane, benzene, toluene, dichloromethane, chloroform, and dichloroethane, preferably one or more of hexane, toluene, and heptane.

[0240] In the present invention, the term "alkyl" means straight-chain alkyl, branched-chain alkyl, or cycloalkyl, examples including, but not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, tert-pentyl, neopentyl, n-hexyl, n-heptyl, n-octyl, n-decyl, cyclopropyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, 4-ethylcyclohexyl, 4-n-propylcyclohexyl, and 4-n-butylcyclohexyl.

[0241] In the present invention, examples of aryls include, but are not limited to, phenyl, 4-methylphenyl, 4-ethylphenyl, dimethylphenyl, and vinylphenyl.

[0242] In the present invention, the term "alkenyl" means straight-chain alkenyl, branched alkenyl, or cycloalkenyl, and examples include, but are not limited to, vinyl, allyl, and butenyl.

[0243] In the present invention, examples of aralkyl include, but are not limited to, phenylmethyl, phenylethyl, phenyl-n-propyl, phenylisopropyl, phenyl-n-butyl, and phenyl-tert-butyl.

[0244] In the present invention, examples of alkalil include, but are not limited to, tolyl, ethylphenyl, n-propylphenyl, isopropylphenyl, n-butylphenyl, and tert-butylphenyl.

[0245] Compared to conventional technology, the present invention has the following advantages:

[0246] 1. The synthesis method of the complex of the present invention is simple and easy to implement, so that a trinuclear complex can be prepared directly from a ligand.

[0247] 2. The catalyst of the present invention can catalyze the polymerization of ethylene with high activity under the action of an organoaluminum or organoboron co-catalyst, and can maintain high polymerization activity, particularly at higher polymerization temperatures (the activity of diimine nickel catalysts reported in previous literature or patents is significantly weakened above 50 degrees and the molecular weight decreases significantly).

[0248] 3. The catalyst of the present invention has superior copolymerization performance with α-olefins or polar monomers.

[0249] Examples

[0250] The present invention is described in detail below with reference to examples; however, it should be understood that the examples are used to illustrate the invention and are not intended to limit the scope of protection of the invention. All reasonable modifications and combinations included within the scope of the inventive concept of the present invention fall within the scope of protection of the present invention.

[0251] The analytical characterization tools and test methods used in the present invention are as follows:

[0252] 1. Nuclear magnetic resonance instrument: Bruker DMX 300 (300 MHz) with tetramethylsilicon (TMS) as an internal standard.

[0253] 2. Molecular weight and molecular weight distribution of the polymer PDI (PDI=Mw / Mn): Measured by PL-GPC220 chromatography with trichlorobenzene as solvent at 150 °C (Standard sample: PS; Flow rate: 1.0 mL / min; Column: 3×PLgel 10 um M1xED-B 300×7.5 nm).

[0254] 3. Activity measurement method: Polymer weight (g) / Nickel (mol) x 2.

[0255] 4. Structural analysis of the complex: Single crystal test analysis using a Rigaku RAXIS Rapid IP diffractometer.

[0256] 5. Analysis of polymer comonomer content: With a polymer sample dissolved in 1,2,4-trichlorobenzene at 120 °C, using a 10 mm PASEX 13 probe, recorded on a 400 MHz Bruker Avance 400 nuclear magnetic resonance spectrometer 1 H NMR and 13 Measured via C NMR spectrum.

[0257] Example 1 - Preparation of Complex Ni1

[0258]

[0259] 0.277 g (0.9 mmol) of (DME)NiBr2 in ethanol (10 mL) The solution was slowly added dropwise to a solution of 0.175 g (0.6 mmol) of ligand L1 in 10 mL of dichloromethane, and the resulting mixture was stirred at room temperature for 6 hours, followed by the addition of anhydrous diethyl ether to precipitate. Filtration was performed to obtain a filter cake, which was washed with anhydrous diethyl ether and dried under vacuum to obtain Ni1 as a yellow powder solid. Yield: 70.2%. Elemental analysis (C 44 H 58 Calculated for Br6N4Ni3O2): C, 39.72; H, 4.39; N, 4.21; Experimental values ​​(%): C, 39.38; H, 4.60; N, 3.96.

[0260] After continuous drying at 130 °C for 6 hours, a 1 L stainless steel polymerization autoclave equipped with mechanical stirring was emptied while hot and refilled with N2 gas three times. 500 mL of hexane was added to the polymerization autoclave, followed by the addition of 5.0 mL of methylaluminoxane (MAO) (a 1.53 mol / l solution in toluene) and 3.3 mg (2.5 μmol) of complex Ni1. The ethylene pressure was maintained at 10 atm, and the reaction was vigorously stirred at 60 °C for 30 minutes. The reaction mixture was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain polyethylene. The results are shown in Table 1 below.

[0261] Example 2

[0262] After continuous drying at 130 °C for 6 hours, a 1 L stainless steel polymerization autoclave equipped with mechanical stirring was emptied while hot and refilled with N2 gas three times. 500 mL of hexane was added to the polymerization autoclave, followed by the addition of 5.0 mL of methylaluminoxane (MAO) (a 1.53 mol / l solution in toluene) and 3.3 mg (2.5 μmol) of complex Ni1. The ethylene pressure was maintained at 10 atm, and the reaction was vigorously stirred at 80 °C for 30 minutes. The reaction mixture was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain polyethylene. The results are shown in Table 1 below.

[0263] Example 3

[0264] After continuous drying at 130 °C for 6 hours, a 1 L stainless steel polymerization autoclave equipped with mechanical stirring was emptied while hot and refilled with N2 gas three times. 500 mL of hexane and 10 mL of 1-hexene were added to the polymerization autoclave, followed by the addition of 5.0 mL of methylaluminoxane (MAO) (a 1.53 mol / l solution in toluene) and 3.3 mg (2.5 μmol) of complex Ni1. The ethylene pressure was maintained at 10 atm, and the reaction was vigorously stirred at 80 °C for 30 minutes. The reaction mixture was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain polyethylene. The results are shown in Table 1 below.

[0265] Example 4

[0266] After continuous drying at 130 °C for 6 hours, a 1 L stainless steel polymerization autoclave equipped with mechanical stirring was emptied while hot and refilled with N2 gas three times. 500 mL of hexane was added to the polymerization autoclave, and simultaneously, 3.3 mg (2.5 μmol) of complex Ni1, 6 mL of 10-undecen-1-ol, 30 mL of AlEt3 (1.0 mol / L solution in hexane), and 5.0 mL of MAO (1.53 mol / L solution in toluene) were added. The ethylene pressure was maintained at 10 atm, and the reaction was stirred at 60 °C for 30 minutes. The reaction mixture was finally neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain the polymer. The polymerization activity and polymer performance parameters are shown in Table 1 below.

[0267] Example 5

[0268] After continuous drying at 130 °C for 6 hours, a 1 L stainless steel polymerization autoclave equipped with mechanical stirring was emptied while hot and refilled with N2 gas three times. 500 mL of hexane was added to the polymerization autoclave, and simultaneously, 3.3 mg (2.5 μmol) of complex Ni1, 5.52 g of 10-undecenatenic acid, 30 mL of AlEt3 (1.0 mol / L solution in hexane), and 5.0 mL of MAO (1.53 mol / L solution in toluene) were added. The ethylene pressure was maintained at 10 atm, and the reaction was stirred at 60 °C for 30 minutes. The reaction mixture was finally neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain the polymer. The polymerization activity and polymer performance parameters are shown in Table 1 below.

[0269] Example 6 - Preparation of Ni2 Complex

[0270]

[0271] 0.277 g (0.9 mmol) of (DME)NiBr2 in ethanol (10 mL) The solution was slowly added dropwise to a solution of 0.246 g (0.6 mmol) of ligand L2 in 10 mL of dichloromethane, and the resulting mixture was stirred at room temperature for 6 hours, followed by the addition of anhydrous diethyl ether to precipitate. Filtration was performed to obtain a filter cake, which was washed with anhydrous diethyl ether and dried under vacuum to obtain Ni2 as a yellow powder solid. Yield: 74.0%. Elemental analysis (C 60 H 90 Calculated for Br6N4Ni3O2): C, 46.35; H, 5.83; N, 3.60; Experimental values ​​(%): C, 46.48; H, 6.12; N, 3.50.

[0272] After continuous drying at 130 °C for 6 hours, a 1 L stainless steel polymerization autoclave equipped with mechanical stirring was emptied while hot and refilled with N2 gas three times. 500 mL of hexane was added to the polymerization autoclave, followed by the addition of 5.0 mL of methylaluminoxane (MAO) (a 1.53 mol / l solution in toluene) and 3.9 mg (2.5 μmol) of complex Ni2. The ethylene pressure was maintained at 10 atm, and the reaction was vigorously stirred at 60 °C for 30 minutes. The reaction mixture was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain polyethylene. The results are shown in Table 1 below.

[0273] Example 7

[0274] After continuous drying at 130 °C for 6 hours, a 1 L stainless steel polymerization autoclave equipped with mechanical stirring was emptied while hot and refilled with N2 gas three times. 500 mL of hexane was added to the polymerization autoclave, followed by the addition of 5.0 mL of methylaluminoxane (MAO) (a 1.53 mol / l solution in toluene) and 3.9 mg (2.5 μmol) of complex Ni2. The ethylene pressure was maintained at 10 atm, and the reaction was vigorously stirred at 80 °C for 30 minutes. The reaction mixture was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain polyethylene. The results are shown in Table 1 below.

[0275] Example 8

[0276] After continuous drying at 130 °C for 6 hours, a 1 L stainless steel polymerization autoclave equipped with mechanical stirring was emptied while hot and refilled with N2 gas three times. 500 mL of hexane and 10 mL of 1-hexene were added to the polymerization autoclave, followed by the addition of 5.0 mL of methylaluminoxane (MAO) (a 1.53 mol / l solution in toluene) and 3.9 mg (2.5 μmol) of complex Ni2. The ethylene pressure was maintained at 10 atm, and the reaction was vigorously stirred at 80 °C for 30 minutes. The reaction mixture was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain polyethylene. The results are shown in Table 1 below.

[0277] Example 9

[0278] After continuous drying at 130 °C for 6 hours, a 1 L stainless steel polymerization autoclave equipped with mechanical stirring was emptied while hot and refilled with N2 gas three times. 500 mL of hexane was added to the polymerization autoclave, and simultaneously, 3.9 mg (2.5 μmol) of complex Ni2, 6 mL of 10-undecen-1-ol, 30 mL of AlEt3 (1.0 mol / L solution in hexane), and 5.0 mL of MAO (1.53 mol / L solution in toluene) were added. The ethylene pressure was maintained at 10 atm, and the reaction was stirred at 60 °C for 30 minutes. The reaction mixture was finally neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain the polymer. The polymerization activity and polymer performance parameters are shown in Table 1 below.

[0279] Example 10

[0280] After continuous drying at 130 °C for 6 hours, a 1 L stainless steel polymerization autoclave equipped with mechanical stirring was emptied while hot and refilled with N2 gas three times. 500 mL of hexane was added to the polymerization autoclave, and simultaneously, 3.9 mg (2.5 μmol) of complex Ni2, 5.52 g of 10-undecenatenic acid, 30 mL of AlEt3 (1.0 mol / L solution in hexane), and 5.0 mL of MAO (1.53 mol / L solution in toluene) were added. The ethylene pressure was maintained at 10 atm, and the reaction was stirred at 60 °C for 30 minutes. The reaction mixture was finally neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain the polymer. The polymerization activity and polymer performance parameters are shown in Table 1 below.

[0281] Example 11 - Preparation of Complex Ni3

[0282]

[0283] 0.277 g (0.9 mmol) of (DME)NiBr2 in 2-methyl-1-propanol (10 mL) The solution was slowly added dropwise to a solution of 0.243 g (0.6 mmol) of ligand L2 in 10 mL of dichloromethane, and the resulting mixture was stirred at room temperature for 6 hours, followed by the addition of anhydrous diethyl ether to precipitate. Filtration was performed to obtain a filter cake, which was washed with anhydrous diethyl ether and dried under vacuum to obtain Ni3 as a yellow powder solid. Yield: 74.5%. Elemental analysis (C 64 H 98 Calculated for Br6N4Ni3O2): C, 47.71; H, 6.13; N, 3.48; Experimental values ​​(%): C, 47.48; H, 6.42; N, 3.29.

[0284] After continuous drying at 130 °C for 6 hours, a 1 L stainless steel polymerization autoclave equipped with mechanical stirring was emptied while hot and refilled with N2 gas three times. 500 mL of hexane was added to the polymerization autoclave, followed by the addition of 5.0 mL of methylaluminoxane (MAO) (a 1.53 mol / l solution in toluene) and 4.0 mg (2.5 μmol) of complex Ni3. The ethylene pressure was maintained at 10 atm, and the reaction was vigorously stirred at 80 °C for 30 minutes. The reaction mixture was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain polyethylene. The results are shown in Table 1 below.

[0285] Example 12 - Preparation of Ni4 Complex

[0286]

[0287] 0.277 g (0.9 mmol) of (DME)NiBr2 in ethanol (10 mL) The solution was slowly added dropwise to a solution of 0.272 g (0.6 mmol) of ligand L3 in 10 mL of dichloromethane. The color of the solution immediately changed to deep red, and a large amount of precipitate was formed. The reaction was stirred at room temperature for 6 hours, followed by the addition of anhydrous diethyl ether to induce precipitation. Filtration was performed to obtain a filter cake, which was washed with anhydrous diethyl ether and dried under vacuum to obtain Ni4 as a brownish-red powder solid. Yield: 74.1%. Elemental analysis (C 64 H 62 Calculated for Br6F4N4Ni3O2): C, 46.57; H, 3.79; N, 3.39; Experimental values ​​(%): C, 46.72; H, 3.97; N, 3.48.

[0288] After continuous drying at 130 °C for 6 hours, a 1 L stainless steel polymerization autoclave equipped with mechanical stirring was emptied while hot and refilled with N2 gas three times. 500 mL of hexane was added to the polymerization autoclave, followed by the addition of 5.0 mL of methylaluminoxane (MAO) (a 1.53 mol / l solution in toluene) and 4.1 mg (2.5 μmol) of complex Ni4. The ethylene pressure was maintained at 10 atm, and the reaction was vigorously stirred at 80 °C for 30 minutes. The reaction mixture was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain polyethylene. The results are shown in Table 1 below.

[0289] Comparative Example 1

[0290] 10 Atm Ethylene: After continuous drying at 130 °C for 6 hours, a 1 L stainless steel polymerization autoclave equipped with mechanical stirring was emptied while hot and refilled with N2 gas three times. 500 mL of hexane was added to the polymerization autoclave, followed by the addition of 5.0 mL of methylaluminoxane (MAO) (a 1.53 mol / l solution in toluene) and 7.7 mg (15 μmol) of catalyst compound A. The ethylene pressure was maintained at 10 atm, and the reaction was vigorously stirred at 60 °C for 30 minutes. The reaction mixture was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain polyethylene. The results are shown in Table 1 below.

[0291] Catalytic compound A

[0292] Comparative Example 2

[0293] After continuous drying at 130 °C for 6 hours, a 1 L stainless steel polymerization autoclave equipped with mechanical stirring was emptied while hot and refilled with N2 gas three times. 500 mL of hexane was added to the polymerization autoclave, followed by the addition of 5.0 mL of methylaluminoxane (MAO) (a 1.53 mol / l solution in toluene) and 7.7 mg (15 μmol) of catalyst compound A. The ethylene pressure was maintained at 10 atm, and the reaction was vigorously stirred at 80 °C for 30 minutes. The reaction mixture was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain polyethylene. The results are shown in Table 1 below.

[0294] Comparative Example 3

[0295] After continuous drying at 130 °C for 6 hours, a 1 L stainless steel polymerization autoclave equipped with mechanical stirring was emptied while hot and refilled with N2 gas three times. 500 mL of hexane and 10 mL of 1-hexene were added to the polymerization autoclave, followed by the addition of 5.0 mL of methylaluminoxane (MAO) (a 1.53 mol / l solution in toluene) and 7.7 mg (15 μmol) of catalyst compound A. The ethylene pressure was maintained at 10 atm, and the reaction was vigorously stirred at 80 °C for 30 minutes. The reaction mixture was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain polyethylene. The results are shown in Table 1 below.

[0296] Examples complex Active (10 6 g / molcat.h) Mw×10 -4 Mw / Mn Example 1 Ni1 3.53 20.9 2.10 Example 2 Ni1 1.27 11.4 2.08 Example 3 Ni1 1.53 11.0 2.03 Example 4 Ni1 3.12 18.4 2.12 Example 5 Ni1 3.21 17.3 2.13 Example 6 Ni2 6.04 70.2 2.04 Example 7 Ni2 3.22 33.1 2.03 Example 8 Ni2 3.41 32.8 2.02 Example 9 Ni2 4.73 48.4 2.10 Example 10 Ni2 4.20 41.6 2.12 Example 11 Ni3 3.02 30.3 2.02 Example 12 Ni4 1.25 8.9 2.06 Comparative Example 1 A 1.96 15.4 2.65 Comparative Example 2 A 0.82 8.3 2.62 Comparative Example 3 A 0.96 8.7 2.57

[0297] In Table 1, compared to the complex of the comparative example, when the metal complex of the present invention is used as the main catalyst, the polymerization activity is higher under high-temperature polymerization conditions, and the molecular weight distribution of the obtained polymer is significantly lower than the molecular weight distribution of the polymer obtained in the comparative example.

[0298] Example 13 - Preparation of Complex Ni5

[0299]

[0300] 0.277 g (0.9 mmol) of (DME)NiBr2 in ethanol (10 mL) The solution was slowly added dropwise to a solution of 0.233 g (0.6 mmol) of ligand L5 in 10 mL of dichloromethane. The color of the solution immediately changed to deep red, and a large amount of precipitate was formed. The reaction was stirred at room temperature for 6 hours, followed by the addition of anhydrous diethyl ether to induce precipitation. Filtration was performed to obtain a filter cake, which was washed with anhydrous diethyl ether and dried under vacuum to obtain Ni5 as a brownish-red powder solid. Yield: 78.2%. Elemental analysis (C 60 H 58 Calculated for Br6N4Ni3O2): C, 47.33; H, 3.84; N, 3.68; Experimental values ​​(%): C, 47.38; H, 4.00; N, 3.46.

[0301] Ethylene polymerization:

[0302] After continuous drying at 130 °C for 6 hours, a 1 L stainless steel polymerization autoclave equipped with mechanical stirring was emptied while hot and refilled with N2 gas three times. 500 mL of hexane was added to the polymerization autoclave, followed by the addition of 6.5 mL of methylaluminoxane (MAO) (a 1.53 mol / l solution in toluene) and 3.8 mg (2.5 μmol) of complex Ni5. The ethylene pressure was maintained at 10 atm, and the reaction was vigorously stirred at 60 °C for 30 minutes. The reaction mixture was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain polyethylene. The results are shown in Table 1 below.

[0303] Example 14

[0304] After continuous drying at 130 °C for 6 hours, a 1 L stainless steel polymerization autoclave equipped with mechanical stirring was emptied while hot and refilled with N2 gas three times. 500 mL of hexane was added to the polymerization autoclave, followed by the addition of 6.5 mL of methylaluminoxane (MAO) (a 1.53 mol / l solution in toluene) and 3.8 mg (2.5 μmol) of complex Ni5. The ethylene pressure was maintained at 10 atm, and the reaction was stirred at 80 °C for 30 minutes. The reaction mixture was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain polyethylene. The results are shown in Table 1 below.

[0305] Example 15

[0306] After continuous drying at 130 °C for 6 hours, a 1 L stainless steel polymerization autoclave equipped with mechanical stirring was emptied while hot and refilled with N2 gas three times. 500 mL of hexane and 10 mL of 1-hexene were added to the polymerization autoclave, followed by the addition of 6.5 mL of methylaluminoxane (MAO) (a 1.53 mol / l solution in toluene) and 3.8 mg (2.5 μmol) of complex Ni5. The ethylene pressure was maintained at 10 atm, and the reaction was vigorously stirred at 80 °C for 30 minutes. The reaction mixture was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain polyethylene. The results are shown in Table 1 below.

[0307] Example 16

[0308] After continuous drying at 130 °C for 6 hours, a 1 L stainless steel polymerization autoclave equipped with mechanical stirring was emptied while hot and refilled with N2 gas three times. 500 mL of hexane was added to the polymerization autoclave, and simultaneously, 3.8 mg (2.5 μmol) of complex Ni5, 6 mL of 10-undecen-1-ol, 30 mL of AlEt3 (1.0 mol / L solution in hexane), and 6.5 mL of MAO (1.53 mol / L solution in toluene) were added. The ethylene pressure was maintained at 10 atm, and the reaction was stirred at 60 °C for 30 minutes. The reaction mixture was finally neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain the polymer. The polymerization activity and polymer performance parameters are shown in Table 1 below.

[0309] Example 17

[0310] After continuous drying at 130 °C for 6 hours, a 1 L stainless steel polymerization autoclave equipped with mechanical stirring was emptied while hot and refilled with N2 gas three times. 500 mL of hexane was added to the polymerization autoclave, and simultaneously, 3.8 mg (2.5 μmol) of complex Ni5, 5.52 g of 10-undecenatenic acid, 30 mL of AlEt3 (1.0 mol / L solution in hexane), and 6.5 mL of MAO (1.53 mol / L solution in toluene) were added. The ethylene pressure was maintained at 10 atm, and the reaction was stirred at 60 °C for 30 minutes. The reaction mixture was finally neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain the polymer. The polymerization activity and polymer performance parameters are shown in Table 1 below.

[0311] Example 18 - Preparation of Complex Ni6

[0312]

[0313] 0.277 g (0.9 mmol) of (DME)NiBr2 in ethanol (10 mL) The solution was slowly added dropwise to a solution of 0.300 g (0.6 mmol) of ligand L6 in 10 mL of dichloromethane. The color of the solution immediately changed to deep red, and a large amount of precipitate was formed. The reaction was stirred at room temperature for 6 hours, followed by the addition of anhydrous diethyl ether to induce precipitation. Filtration was performed to obtain a filter cake, which was washed with anhydrous diethyl ether and dried under vacuum to obtain Ni6 as a brownish-red powder solid. Yield: 74.0%. Elemental analysis (C 76 H 90 Calculated for Br6N4Ni3O2): C, 52.25; H, 5.19; N, 3.21; Experimental values ​​(%): C, 52.48; H, 5.52; N, 3.10.

[0314] After continuous drying at 130 °C for 6 hours, a 1 L stainless steel polymerization autoclave equipped with mechanical stirring was emptied while hot and refilled with N2 gas three times. 500 mL of hexane was added to the polymerization autoclave, followed by the addition of 6.5 mL of methylaluminoxane (MAO) (a 1.53 mol / l solution in toluene) and 4.4 mg (2.5 μmol) of complex Ni6. The ethylene pressure was maintained at 10 atm, and the reaction was vigorously stirred at 60 °C for 30 minutes. The reaction mixture was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain polyethylene. The results are shown in Table 2 below.

[0315] Example 19

[0316] After continuous drying at 130 °C for 6 hours, a 1 L stainless steel polymerization autoclave equipped with mechanical stirring was emptied while hot and refilled with N2 gas three times. 500 mL of hexane was added to the polymerization autoclave, followed by the addition of 6.5 mL of methylaluminoxane (MAO) (a 1.53 mol / l solution in toluene) and 4.4 mg (2.5 μmol) of complex Ni6. The ethylene pressure was maintained at 10 atm, and the reaction was vigorously stirred at 80 °C for 30 minutes. The reaction mixture was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain polyethylene. The results are shown in Table 2 below.

[0317] Example 20

[0318] After continuous drying at 130 °C for 6 hours, a 1 L stainless steel polymerization autoclave equipped with mechanical stirring was emptied while hot and refilled with N2 gas three times. 500 mL of hexane and 10 mL of 1-hexene were added to the polymerization autoclave, followed by the addition of 6.5 mL of methylaluminoxane (MAO) (a 1.53 mol / l solution in toluene) and 4.4 mg (2.5 μmol) of complex Ni6. The ethylene pressure was maintained at 10 atm, and the reaction was vigorously stirred at 80 °C for 30 minutes. The reaction mixture was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain the polymer. The results are shown in Table 2 below.

[0319] Example 21

[0320] After continuous drying at 130 °C for 6 hours, a 1 L stainless steel polymerization autoclave equipped with mechanical stirring was emptied while hot and refilled with N2 gas three times. 500 mL of hexane was added to the polymerization autoclave, and simultaneously, 4.4 mg (2.5 μmol) of complex Ni6, 6 mL of 10-undecen-1-ol, 30 mL of AlEt3 (1.0 mol / L solution in hexane), and 6.5 mL of MAO (1.53 mol / L solution in toluene) were added. The ethylene pressure was maintained at 10 atm, and the reaction was stirred at 60 °C for 30 minutes. The reaction mixture was finally neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain the polymer. The polymerization activity and polymer performance parameters are shown in Table 2 below.

[0321] Example 22

[0322] After continuous drying at 130 °C for 6 hours, a 1 L stainless steel polymerization autoclave equipped with mechanical stirring was emptied while hot and refilled with N2 gas three times. 500 mL of hexane was added to the polymerization autoclave, and simultaneously, 4.4 mg (2.5 μmol) of complex Ni6, 5.52 g of 10-undecenatenic acid, 30 mL of AlEt3 (1.0 mol / L solution in hexane), and 6.5 mL of MAO (1.53 mol / L solution in toluene) were added. The ethylene pressure was maintained at 10 atm, and the reaction was stirred at 60 °C for 30 minutes. The reaction mixture was finally neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain the polymer. The polymerization activity and polymer performance parameters are shown in Table 2 below.

[0323] Example 23 - Preparation of Complex Ni7

[0324]

[0325] 0.277 g (0.9 mmol) of (DME)NiBr2 in 2-methyl-1-propanol (10 mL) The solution was slowly added dropwise to a solution of 0.300 g (0.6 mmol) of ligand L2 in 10 mL of dichloromethane. The color of the solution immediately changed to deep red, and a large amount of precipitate was formed. The reaction was stirred at room temperature for 6 hours, followed by the addition of anhydrous diethyl ether to induce precipitation. Filtration was performed to obtain a filter cake, which was washed with anhydrous diethyl ether and dried under vacuum to obtain Ni4 as a brownish-red powder solid. Yield: 74.0%. Elemental analysis (C 80 H 98 Calculated for Br6N4Ni3O2): C, 53.29; H, 5.48; N, 3.11; Experimental values ​​(%): C, 53.28; H, 5.82; N, 3.29.

[0326] Ethylene polymerization:

[0327] After continuous drying at 130 °C for 6 hours, a 1 L stainless steel polymerization autoclave equipped with mechanical stirring was emptied while hot and refilled with N2 gas three times. 500 mL of hexane was added to the polymerization autoclave, followed by the addition of 6.5 mL of methylaluminoxane (MAO) (a 1.53 mol / l solution in toluene) and 4.5 mg (2.5 μmol) of complex Ni7. The ethylene pressure was maintained at 10 atm, and the reaction was vigorously stirred at 60 °C for 30 minutes. The reaction mixture was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain polyethylene. The results are shown in Table 2 below.

[0328] Example 24 - Preparation of Complex Ni8

[0329]

[0330] 0.277 g (0.9 mmol) of (DME)NiBr2 in ethanol (10 mL) The solution was slowly added dropwise to a solution of 0.389 g (0.6 mmol) of ligand L7 in 10 mL of dichloromethane. The color of the solution immediately changed to deep red, and a large amount of precipitate was formed. The reaction was stirred at room temperature for 6 hours, followed by the addition of anhydrous diethyl ether to induce precipitation. Filtration was performed to obtain a filter cake, which was washed with anhydrous diethyl ether and dried under vacuum to obtain Ni8 as a brownish-red powder solid. Yield: 74.1%. Elemental analysis (C 52 H 34 Br 14 Calculated for N4Ni3O2): C, 30.59; H, 1.68; N, 2.74; Experimental values ​​(%): C, 30.72; H, 1.97; N, 2.48.

[0331] Ethylene polymerization:

[0332] After continuous drying at 130 °C for 6 hours, a 1 L stainless steel polymerization autoclave equipped with mechanical stirring was emptied while hot and refilled with N2 gas three times. 500 mL of hexane was added to the polymerization autoclave, followed by the addition of 6.5 mL of methylaluminoxane (MAO) (a 1.53 mol / l solution in toluene) and 5.1 mg (2.5 μmol) of complex Ni8. The ethylene pressure was maintained at 10 atm, and the reaction was vigorously stirred at 60 °C for 30 minutes. The reaction mixture was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain polyethylene. The results are shown in Table 2 below.

[0333] Example 25 - Preparation of Complex Ni9

[0334]

[0335] 0.277 g (0.9 mmol) of (DME)NiBr2 in ethanol (10 mL) The solution was slowly added dropwise to a solution of 0.249 g (0.6 mmol) of ligand L8 in 10 mL of dichloromethane. The color of the solution immediately changed to deep red, and a large amount of precipitate was formed. The reaction was stirred at room temperature for 6 hours, followed by the addition of anhydrous diethyl ether to induce precipitation. Filtration was performed to obtain a filter cake, which was washed with anhydrous diethyl ether and dried under vacuum to obtain Ni9 as a brownish-red powder solid. Yield: 78.6%. Elemental analysis (C 64 H 66 Calculated for Br6N4Ni3O2): C, 48.69; H, 4.21; N, 3.55; Experimental values ​​(%): C, 48.54; H, 4.47; N, 3.21.

[0336] Ethylene polymerization:

[0337] After continuous drying at 130 °C for 6 hours, a 1 L stainless steel polymerization autoclave equipped with mechanical stirring was emptied while hot and refilled with N2 gas three times. 500 mL of hexane was added to the polymerization autoclave, followed by the addition of 6.5 mL of methylaluminoxane (MAO) (a 1.53 mol / l solution in toluene) and 3.9 mg (2.5 μmol) of complex Ni9. The ethylene pressure was maintained at 10 atm, and the reaction was vigorously stirred at 60 °C for 30 minutes. The reaction mixture was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain polyethylene. The results are shown in Table 2 below.

[0338] Example 26 - Complex Ni 10 manufacturing

[0339]

[0340] 0.277 g (0.9 mmol) of (DME)NiBr2 in ethanol (10 mL) The solution was slowly added dropwise to a solution of 0.317 g (0.6 mmol) of ligand L9 in 10 mL of dichloromethane. The color of the solution immediately changed to deep red, and a large amount of precipitate was formed. The reaction was stirred at room temperature for 6 hours, followed by the addition of anhydrous diethyl ether to induce precipitation. Filtration was performed to obtain a filter cake, which was washed with anhydrous diethyl ether and dried under vacuum to obtain Ni 10 It was obtained as a brownish-red powder solid. Yield: 75.2%. Elemental analysis (C 80 H 98 Calculated for Br6N4Ni3O2): C, 53.29; H, 5.48; N, 3.11; Experimental values ​​(%): C, 53.62; H, 5.87; N, 3.00.

[0341] Ethylene polymerization:

[0342] After continuous drying at 130 °C for 6 hours, a 1 L stainless steel polymerization autoclave equipped with mechanical stirring was emptied while hot and refilled with N2 gas three times. 500 mL of hexane was added to the polymerization autoclave, followed by the addition of 6.5 mL of methylaluminoxane (MAO) (1.53 mol / l solution in toluene) and 4.5 mg (2.5 μmol) of complex Ni 10 Ethylene was added. The ethylene pressure was maintained at 10 atm, and the reaction was vigorously stirred at 60°C for 30 minutes. The reaction mixture was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain polyethylene. The results are shown in Table 2 below.

[0343] Comparative Example 4

[0344] After continuous drying at 130 °C for 6 hours, a 1 L stainless steel polymerization autoclave equipped with mechanical stirring was emptied while hot and refilled with N2 gas three times. 500 mL of hexane was added to the polymerization autoclave, followed by the addition of 6.5 mL of methylaluminoxane (MAO) (a 1.53 mol / l solution in toluene) and 4.6 mg (7.5 μmol) of catalyst compound B. The ethylene pressure was maintained at 10 atm, and the reaction was vigorously stirred at 60 °C for 30 minutes. The reaction mixture was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain polyethylene. The results are shown in Table 2 below.

[0345] Catalytic compound B

[0346] Comparative Example 5

[0347] After continuous drying at 130 °C for 6 hours, a 1 L stainless steel polymerization autoclave equipped with mechanical stirring was emptied while hot and refilled with N2 gas three times. 500 mL of hexane was added to the polymerization autoclave, followed by the addition of 6.5 mL of methylaluminoxane (MAO) (a 1.53 mol / l solution in toluene) and 4.6 mg (7.5 μmol) of catalyst compound B. The ethylene pressure was maintained at 10 atm, and the reaction was vigorously stirred at 80 °C for 30 minutes. The reaction mixture was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain polyethylene. The results are shown in Table 2 below.

[0348] Comparative Example 6

[0349] After continuous drying at 130 °C for 6 hours, a 1 L stainless steel polymerization autoclave equipped with mechanical stirring was emptied while hot and refilled with N2 gas three times. 500 mL of hexane and 10 mL of 1-hexene were added to the polymerization autoclave, followed by the addition of 6.5 mL of methylaluminoxane (MAO) (a 1.53 mol / l solution in toluene) and 4.6 mg (7.5 μmol) of catalyst compound B. The ethylene pressure was maintained at 10 atm, and the reaction was vigorously stirred at 80 °C for 30 minutes. The reaction mixture was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain polyethylene. The results are shown in Table 2 below.

[0350] Examples complex Active (10 6 g / molcat.h) Mw×10 -4 Mw / Mn Example 13 Ni5 11.4 10.3 2.08 Example 14 Ni5 4.2 6.7 2.09 Example 15 Ni5 5.1 6.9 2.06 Example 16 Ni5 10.6 10.4 2.12 Example 17 Ni5 10.2 9.3 2.16 Example 18 Ni6 22.9 41.2 2.03 Example 19 Ni6 13.6 22.7 2.04 Example 20 Ni6 14.4 21.9 2.04 Example 21 Ni6 16.3 33.8 2.10 Example 22 Ni6 15.2 31.2 2.16 Example 23 Ni7 18.1 40.4 2.02 Example 24 Ni8 10.3 14.8 2.07 Example 25 Ni9 13.6 8.6 2.03 Example 26 In 10 19.4 37.2 2.06 Comparative Example 4 B 9.6 9.3 2.40 Comparative Example 5 B 3.7 6.0 2.32 Comparative Example 6 B 4.3 6.2 2.37

[0351] In Table 2, compared to the complex of the comparative example, when the metal complex of the present invention is used as the main catalyst, the polymerization activity under high-temperature polymerization conditions is much higher, and the molecular weight distribution of the obtained polymer is significantly lower than the molecular weight distribution of the polymer obtained in the comparative example.

[0352] The structural chemical formulas of the complexes associated with the following Examples 27-40 are as follows:

[0353] Chemical formula IIIb

[0354] Example 27 - Complex Ni 11 Preparation of (represented by structural formula IIIb, where R 1 , R 3 is ethyl; R 2 , R 4 -R 7 , R 10 is hydrogen; R 8 , R 9 and R 11 is methyl; R 12 is ethyl; M is nickel, Y is O, and X is Br):

[0355] Under a nitrogen atmosphere, 2,6-diethylaniline (2.0 ml, 12 mmol) was dissolved in 20 ml of toluene, and 12 ml of trimethylaluminum (1.0 M, 12 mmol) was added dropwise at room temperature. The reaction was refluxed for 2 hours, and then the system was cooled to room temperature. Campoquinone (0.831 g, 5 mmol) was added, and the system was refluxed for 6 hours. The reaction product was neutralized with an aqueous sodium hydroxide solution, extracted with dichloromethane, dried, and then column chromatographed to obtain the yellow ligand L 10 ...was obtained. Yield: 69.2%. 1 H-NMR (CDCl3): δ 6.94-6.92 (m, 6H, C Ar -CH3), 2.56-2.51 (m, 4H, C Ar -CH3), 2.36-2.31 (m, 4H, C Ar -CH3), 1.82-1.78 (m, 4H, CH2), 1.54 (m, 1H), 1.24-1.18 (m, 12H), 1.09 (s, 3H, CH3), 0.94 (m, 6H, CH3).

[0356] 0.277 g (0.9 mmol) of (DME)NiBr2 in ethanol (10 mL) A solution of 0.258 g (0.6 mmol) of ligand L in dichloromethane (10 mL). 10 It was slowly added dropwise to the solution. The color of the solution immediately changed to deep red, and a large amount of precipitate was formed. The reaction was stirred at room temperature for 6 hours, followed by the addition of anhydrous diethyl ether to induce precipitation. Filtration was performed to obtain a filter cake, which was washed with anhydrous diethyl ether and dried under vacuum to obtain Ni4 as a brownish-red powder solid. Yield: 78.2%. Elemental analysis (C 64 H 90Calculated for Br6N4Ni3O2): C, 47.96; H, 5.66; N, 3.50; Experimental values ​​(%): C, 47.48; H, 6.00; N, 3.26.

[0357] Ethylene polymerization:

[0358] After continuous drying at 130 °C for 6 hours, a 1 L stainless steel polymerization autoclave equipped with mechanical stirring was emptied while hot and refilled with N2 gas three times. 500 mL of hexane was added to the polymerization autoclave, followed by the addition of 5.0 mL of methylaluminoxane (MAO) (1.53 mol / l solution in toluene) and 4.0 mg (2.5 μmol) of complex Ni 11 ethylene was added. The ethylene pressure was maintained at 10 atm, and the reaction was vigorously stirred at 60°C for 30 minutes. The reaction mixture was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain polyethylene. The results are shown in Table 3 below.

[0359] Example 28

[0360] After continuous drying at 130 °C for 6 hours, a 1 L stainless steel polymerization autoclave equipped with mechanical stirring was emptied while hot and refilled with N2 gas three times. 500 mL of hexane was added to the polymerization autoclave, followed by the addition of 5.0 mL of methylaluminoxane (MAO) (1.53 mol / l solution in toluene) and 4.0 mg (2.5 μmol) of complex Ni 11 Ethylene was added. The ethylene pressure was maintained at 10 atm, and the reaction was vigorously stirred at 100°C for 30 minutes. The reaction mixture was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain polyethylene. The results are shown in Table 3 below.

[0361] Example 3

[0362] After continuous drying at 130 °C for 6 hours, a 1 L stainless steel polymerization autoclave equipped with mechanical stirring was emptied while hot and refilled with N2 gas three times. 500 mL of hexane and 10 mL of 1-hexene were added to the polymerization autoclave, followed by the addition of 5.0 mL of methylaluminoxane (MAO) (1.53 mol / l solution in toluene) and 4.0 mg (2.5 μmol) of complex Ni 11 Ethylene was added. The ethylene pressure was maintained at 10 atm, and the reaction was vigorously stirred at 100°C for 30 minutes. The reaction mixture was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain polyethylene. The results are shown in Table 3 below.

[0363] Example 29

[0364] After drying continuously at 130 ℃ for 6 hours, the 1L stainless steel polymerization autoclave equipped with mechanical stirring was emptied while hot and filled with N2 gas 3 times.

[0365] 500 mL of hexane was filled into a polymerization autoclave, and at the same time, 4.0 mg (2.5 μmol) of complex Ni 11 6 mL of 10-undecen-1-ol, 30 mL of AlEt3 (1.0 mol / L solution in hexane), and 5.0 mL of MAO (1.53 mol / L solution in toluene) were added to this. The ethylene pressure was maintained at 10 atm, and the reaction was stirred at 60 °C for 30 minutes. The reaction mixture was finally neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain the polymer. The polymerization activity and polymer performance parameters are shown in Table 3 below.

[0366] Example 30

[0367] After continuous drying at 130 °C for 6 hours, a 1 L stainless steel polymerization autoclave equipped with mechanical stirring was emptied while hot and refilled with N2 gas three times. 500 mL of hexane was added to the polymerization autoclave, and simultaneously, 4.0 mg (2.5 μmol) of the complex Ni 11 5.52 g of 10-undecenatenic acid, 30 mL of AlEt3 (1.0 mol / L solution in hexane), and 5.0 mL of MAO (1.53 mol / L solution in toluene) were added to this. The ethylene pressure was maintained at 10 atm, and the reaction was stirred at 60 °C for 30 minutes. The reaction mixture was finally neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain the polymer. The polymerization activity and polymer performance parameters are shown in Table 3 below.

[0368] Example 31 - Complex Ni 12 Preparation of (represented by structural formula IIIb, where R 1 , R 3 is isopropyl and; R 2 , R 4 -R 7 , R 10 is hydrogen; R 8 , R 9 and R 11 is methyl; R 12 is ethyl; M is nickel, Y is O, and X is Br):

[0369] Under a nitrogen atmosphere, 2,6-diisopropylaniline (2.4 ml, 12 mmol) was dissolved in 20 ml of toluene, and 12 ml of trimethylaluminum (1.0 M, 12 mmol) was added dropwise at room temperature. The reaction was refluxed for 2 hours, and then the system was cooled to room temperature. Campoquinone (0.831 g, 5 mmol) was added, and the system was refluxed for 6 hours. The reaction product was neutralized with an aqueous sodium hydroxide solution, extracted with dichloromethane, dried, and then column chromatographed to obtain the yellow ligand L 11 ...was obtained. Yield: 41.3%. 1 H NMR (300 MHz, CDCl3), δ (ppm): 7.06-6.81 (m, 6H, Ar-H), 2.88 (m, 4H, CH(CH3)2), 2.36 (m, 1H), 1.86 (m, 4H, CH2), 1.24 (d, 24H, CH(CH3)2), 0.96 (s, 6H, CH3at camphyl), 0.77 (s, 3H, CH3).

[0370] 0.277 g (0.9 mmol) of (DME)NiBr2 in ethanol (10 mL) A solution of 0.291 g (0.6 mmol) of ligand L in dichloromethane (10 mL). 11 It was slowly added dropwise to the solution. The color of the solution immediately changed to deep red, and a large amount of precipitate was formed. The reaction was stirred at room temperature for 6 hours, and then anhydrous diethyl ether was added to induce precipitation. Filtration was performed to obtain a filter cake, the filter cake was washed with anhydrous diethyl ether, and dried under vacuum to obtain Ni 12 was obtained as a brownish-red powder solid. Yield: 74.0%. Elemental analysis (C 72 H 106Calculated for Br6N4Ni3O2): C, 50.42; H, 6.23; N, 3.27; Experimental values ​​(%): C, 50.28; H, 6.42; N, 3.18.

[0371] After continuous drying at 130 °C for 6 hours, a 1 L stainless steel polymerization autoclave equipped with mechanical stirring was emptied while hot and refilled with N2 gas three times. 500 mL of hexane was added to the polymerization autoclave, followed by the addition of 5.0 mL of methylaluminoxane (MAO) (1.53 mol / l solution in toluene) and 4.3 mg (2.5 μmol) of complex Ni 12 ...was added. The ethylene pressure was maintained at 10 atm, and the reaction was vigorously stirred at 60°C for 30 minutes. The reaction mixture was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain polyethylene. The results are shown in Table 3 below.

[0372] Example 32

[0373] After continuous drying at 130 °C for 6 hours, a 1 L stainless steel polymerization autoclave equipped with mechanical stirring was emptied while hot and refilled with N2 gas three times. 500 mL of hexane was added to the polymerization autoclave, followed by the addition of 5.0 mL of methylaluminoxane (MAO) (1.53 mol / l solution in toluene) and 4.3 mg (2.5 μmol) of complex Ni 12 ...was added. The ethylene pressure was maintained at 10 atm, and the reaction was vigorously stirred at 100°C for 30 minutes. The reaction mixture was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain polyethylene. The results are shown in Table 3 below.

[0374] Example 33

[0375] After continuous drying at 130 °C for 6 hours, a 1 L stainless steel polymerization autoclave equipped with mechanical stirring was emptied while hot and refilled with N2 gas three times. 500 mL of hexane and 10 mL of 1-hexene were added to the polymerization autoclave, followed by the addition of 5.0 mL of methylaluminoxane (MAO) (1.53 mol / l solution in toluene) and 4.3 mg (2.5 μmol) of complex Ni 12 ...was added. The ethylene pressure was maintained at 10 atm, and the reaction was vigorously stirred at 100°C for 30 minutes. The reaction mixture was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain a polymer. The results are shown in Table 3 below.

[0376] Example 34

[0377] After continuous drying at 130 °C for 6 hours, a 1 L stainless steel polymerization autoclave equipped with mechanical stirring was emptied while hot and refilled with N2 gas three times. 500 mL of hexane was added to the polymerization autoclave, and simultaneously, 4.3 mg (2.5 μmol) of the complex Ni 12 6 mL of 10-undecen-1-ol, 30 mL of AlEt3 (1.0 mol / L solution in hexane), and 5.0 mL of MAO (1.53 mol / L solution in toluene) were added to this. The ethylene pressure was maintained at 10 atm, and the reaction was stirred at 60 °C for 30 minutes. The reaction mixture was finally neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain the polymer. The polymerization activity and polymer performance parameters are shown in Table 3 below.

[0378] Example 35

[0379] After continuous drying at 130 °C for 6 hours, a 1 L stainless steel polymerization autoclave equipped with mechanical stirring was emptied while hot and refilled with N2 gas three times. 500 mL of hexane was added to the polymerization autoclave, and simultaneously, 4.3 mg (2.5 μmol) of the complex Ni 12 5.52 g of 10-undecenatenic acid, 30 mL of AlEt3 (1.0 mol / L solution in hexane), and 5.0 mL of MAO (1.53 mol / L solution in toluene) were added to this. The ethylene pressure was maintained at 10 atm, and the reaction was stirred at 60 °C for 30 minutes. The reaction mixture was finally neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain the polymer. The polymerization activity and polymer performance parameters are shown in Table 3 below.

[0380] Example 36 - Complex Ni 13 Preparation of (represented by structural formula IIIb, where R 1 , R 3 is isopropyl and; R 2 , R 4 -R 7 , R 10 is hydrogen; R 8 , R 9 and R 11 is methyl; R 12 is isobutyl; M is nickel, Y is O, and X is Br):

[0381] 0.277 g (0.9 mmol) of (DME)NiBr2 in 2-methyl-1-propanol (10 mL) A solution of 0.291 g (0.6 mmol) of ligand L in dichloromethane (10 mL). 11It was slowly added dropwise to the solution. The color of the solution immediately changed to deep red, and a large amount of precipitate was formed. The reaction was stirred at room temperature for 6 hours, and then anhydrous diethyl ether was added to induce precipitation. Filtration was performed to obtain a filter cake, the filter cake was washed with anhydrous diethyl ether, and dried under vacuum to obtain Ni 13 It was obtained as a brownish-red powder solid. Yield: 74.0%. Elemental analysis (C 76 H 114 Calculated for Br6N4Ni3O2): C, 51.54; H, 6.49; N, 3.16; Experimental values ​​(%): C, 51.28; H, 6.82; N, 3.19.

[0382] Ethylene Polymerization: After continuous drying at 130 °C for 6 hours, a 1 L stainless steel polymerization autoclave equipped with mechanical stirring was emptied while hot and refilled with N2 gas three times. 500 mL of hexane was added to the polymerization autoclave, followed by the addition of 5.0 mL of methylaluminoxane (MAO) (1.53 mol / l solution in toluene) and 4.4 mg (2.5 μmol) of complex Ni 13 Ethylene was added. The ethylene pressure was maintained at 10 atm, and the reaction was vigorously stirred at 100°C for 30 minutes. The reaction mixture was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain polyethylene. The results are shown in Table 3 below.

[0383] Example 37 - Complex Ni 14 Preparation of (represented by structural formula IIIb, where R 1 , R 3 is fluorine; R 2 , R 4 -R 7 , R 10 is hydrogen; R 8 , R 9 and R 11 is methyl; R 12is ethyl; M is nickel, Y is O, and X is Br):

[0384] Under a nitrogen atmosphere, 2,6-difluoroaniline (1.3 ml, 12 mmol) was dissolved in 20 ml of toluene, and 12 ml of trimethylaluminum (1.0 M, 12 mmol) was added dropwise at room temperature. The reaction was refluxed for 2 hours, and then the system was cooled to room temperature. Campoquinone (0.831 g, 5 mmol) was added, and the system was refluxed for 6 hours. The reaction product was neutralized with an aqueous sodium hydroxide solution, extracted with dichloromethane, dried, and then column chromatographed to obtain the yellow ligand L 12 was obtained. Yield: 50.3%. 1 HNMR (CDCl3): δ [1.2:1 isomer ratio]: major isomer: 6.83-6.74 (m, 6H, C Ar -CH3), 1.93-1.90 (m, 4H, CH2), 1.55 (m, 1Hl), 1.26 (s, 3H, CH3), 1.06 (s, 6H, CH3), minor isomer: 6.91-6.84 (m, 6H, C Ar -CH3), 1.96-1.94 (m, 4H, CH2), 1.55 (m, 1H,), 1.26 (s, 3H, CH3), 1.02 (s, 6H, CH3).

[0385] 0.277 g (0.9 mmol) of (DME)NiBr2 in ethanol (10 mL) A solution of 0.233 g (0.6 mmol) of ligand L in dichloromethane (10 mL). 12It was slowly added dropwise to the solution. The color of the solution immediately changed to deep red, and a large amount of precipitate was formed. The reaction was stirred at room temperature for 6 hours, and then anhydrous diethyl ether was added to induce precipitation. Filtration was performed to obtain a filter cake, the filter cake was washed with anhydrous diethyl ether, and dried under vacuum to obtain Ni 14 was obtained as a brownish-red powder solid. Yield: 74.3%. Elemental analysis (C 48 H 50 Calculated for Br6F8N4Ni3O2): C, 37.87; H, 3.31; N, 3.68; Experimental values ​​(%): C, 37.78; H, 3.62; N, 3.28.

[0386] Ethylene Polymerization: After continuous drying at 130 °C for 6 hours, a 1 L stainless steel polymerization autoclave equipped with mechanical stirring was emptied while hot and refilled with N2 gas three times. 500 mL of hexane was added to the polymerization autoclave, followed by the addition of 5.0 mL of methylaluminoxane (MAO) (1.53 mol / l solution in toluene) and 3.8 mg (2.5 μmol) of complex Ni 14 ...was added. The ethylene pressure was maintained at 10 atm, and the reaction was vigorously stirred at 60°C for 30 minutes. The reaction mixture was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain polyethylene. The results are shown in Table 3 below.

[0387] Example 38 - Complex Ni 15 Preparation of (represented by structural formula IIIb, where R 1 -R 3 is methyl, and R 4 -R 7 and R 10 is hydrogen, and R 8 , R 9 and R 11 is methyl, and R 12is ethyl, M is nickel, Y is O, and X is Br):

[0388] Under a nitrogen atmosphere, 2,4,6-trimethylaniline (1.7 ml, 12 mmol) was dissolved in 20 ml of toluene, and 12 ml of trimethylaluminum (1.0 M, 12 mmol) was added dropwise at room temperature. The reaction was refluxed for 2 hours, and then the system was cooled to room temperature. Campoquinone (0.831 g, 5 mmol) was added, and the system was refluxed for 6 hours. The reaction product was neutralized with an aqueous sodium hydroxide solution, extracted with dichloromethane, dried, and then column chromatographed to obtain the yellow ligand L 13 ...was obtained. Yield: 62.5%. 1 HNMR (300 MHz, CDCl3), δ (ppm) [Isomer ratio of 1.2:1]: Major isomers: 6.72 (s, 4H, Ar-H), 2.26-2.13 (m, 12H, C Ar -CH3), 1.87 (s, 6H, C Ar -CH3), 1.79 (m, 4H, CH2), 1.42 (m, 1H), 1.26 (s, 3H, CH3), 1.07 (s, 6H, CH3); Negative isomer: 6.67 (s, 4H, Ar-H), 2.09-2.01 (m, 12H, C Ar -CH3), 1.85 (s, 6H, C Ar -CH3), 1.79 (m, 4H, CH2), 1.40 (m, 1H), 1.26 (s, 3H, CH3), 0.94 (s, 6H, CH3).

[0389] 0.277 g (0.9 mmol) of (DME)NiBr2 in ethanol (10 mL) A solution of 0.240 g (0.6 mmol) of ligand L in dichloromethane (10 mL). 13It was slowly added dropwise to the solution. The color of the solution immediately changed to deep red, and a large amount of precipitate was formed. The reaction was stirred at room temperature for 6 hours, and then anhydrous diethyl ether was added to induce precipitation. Filtration was performed to obtain a filter cake, the filter cake was washed with anhydrous diethyl ether, and dried under vacuum to obtain Ni 15 was obtained as a brownish-red powder solid. Yield: 78.6%. Elemental analysis (C 60 H 82 Calculated for Br6N4Ni3O2): C, 46.59; H, 5.34; N, 3.62; Experimental values ​​(%): C, 46.24; H, 5.67; N, 3.21.

[0390] Ethylene Polymerization: After continuous drying at 130 °C for 6 hours, a 1 L stainless steel polymerization autoclave equipped with mechanical stirring was emptied while hot and refilled with N2 gas three times. 500 mL of hexane was added to the polymerization autoclave, followed by the addition of 5.0 mL of methylaluminoxane (MAO) (1.53 mol / l solution in toluene) and 3.9 mg (2.5 μmol) of complex Ni 15 ...was added. The ethylene pressure was maintained at 10 atm, and the reaction was vigorously stirred at 60°C for 30 minutes. The reaction mixture was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain polyethylene. The results are shown in Table 3 below.

[0391] Example 39 - Complex Ni 16 Preparation of (represented by structural formula IIIb, where R 1 and R 3 is methyl, and R 2 is bromine, and R 4 -R 7 and R 10 is hydrogen, and R 8 , R 9 and R 11 is methyl, and R 12is ethyl, M is nickel, Y is O, and X is Br):

[0392] Under a nitrogen atmosphere, 2,6-dimethyl-4-bromo-aniline (2.45 g, 12 mmol) was dissolved in 20 ml of toluene, and 12 ml of trimethylaluminum (1.0 M, 12 mmol) was added dropwise at room temperature. The reaction was refluxed for 2 hours, and then the system was cooled to room temperature. Campoquinone (0.831 g, 5 mmol) was added, and the system was refluxed for 6 hours. The reaction product was neutralized with an aqueous sodium hydroxide solution, extracted with dichloromethane, dried, and then column chromatographed to obtain the yellow ligand L 14 was obtained. Yield: 60.7%. 1 HNMR (300 MHz, CDCl3), δ (ppm) [1.1:1 isomer ratio]: Major isomers: 7.05 (s, 4H, Ar-H), 2.18 (m, 12H, C Ar -CH3), 1.85 (m, 4H, CH2), 1.37 (m, 1H), 1.26 (s, 3H, CH3), 1.06 (s, 6H, CH3); Negative isomers: 7.02 (s, 4H, Ar-H), 2.04 (m, 12H, C Ar -CH3), 1.85 (m, 4H, CH2), 1.37 (m, 1H), 1.26 (s, 3H, CH3), 0.96 (s, 6H, CH3).

[0393] 0.278 g (0.9 mmol) of (DME)NiBr2 in ethanol (10 mL) A solution of 0.318 g (0.6 mmol) of ligand L in dichloromethane (10 mL). 14It was slowly added dropwise to the solution. The color of the solution immediately changed to deep red, and a large amount of precipitate was formed. The reaction was stirred at room temperature for 6 hours, and then anhydrous diethyl ether was added to induce precipitation. Filtration was performed to obtain a filter cake, the filter cake was washed with anhydrous diethyl ether, and dried under vacuum to obtain Ni 16 It was obtained as a brownish-red powder solid. Yield: 74.1%. Elemental analysis (C 56 H 70 Br 10 Calculated for N4Ni3O2): C, 37.24; H, 3.91; N, 3.10; Experimental values ​​(%): C, 37.38; H, 4.30; N, 3.03.

[0394] Ethylene Polymerization: After continuous drying at 130 °C for 6 hours, a 1 L stainless steel polymerization autoclave equipped with mechanical stirring was emptied while hot and refilled with N2 gas three times. 500 mL of hexane was added to the polymerization autoclave, followed by the addition of 5.0 mL of methylaluminoxane (MAO) (1.53 mol / l solution in toluene) and 4.5 mg (2.5 μmol) of complex Ni 16 ethylene was added. The ethylene pressure was maintained at 10 atm, and the reaction was vigorously stirred at 60°C for 30 minutes. The reaction mixture was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain polyethylene. The results are shown in Table 3 below.

[0395] Example 40 - Complex Ni 17 Preparation of (represented by structural formula IIIb, where R 1 and R 3 is isopropyl, and R 2 , R 4 -R 7 and R 10 is hydrogen, and R 8 and R 9 is methyl, and R 11is CH2Br, and R 12 is ethyl):

[0396] Under a nitrogen atmosphere, 2,6-diisopropyl-aniline (2.30 ml, 12 mmol) was dissolved in 20 ml of toluene, and 12 ml of trimethylaluminum (1.0 M, 12 mmol) was added dropwise at room temperature. The reaction was refluxed for 2 hours, and then the system was cooled to room temperature. Dione (1.225 g, 5 mmol) was added, and the system was refluxed for 6 hours. The reaction product was neutralized with an aqueous sodium hydroxide solution, extracted with dichloromethane, dried, and then column chromatographed to obtain the yellow ligand L. 15 was obtained. Yield: 62.7%. 1 H NMR (300 MHz, CDCl3), δ (ppm): 7.05-6.83 (m, 6H, Ar-H), 3.30 (m, 2H, CH2), 2.80 (m, 4H, CH(CH3)2), 1.55 (m, 1H), 1.83 (m, 4H, CH2), 1.26 (d, 24H, CH(CH3)2), 0.99 (s, 6H, CH3).

[0397] 0.277 g (0.9 mmol) of (DME)NiBr2 in ethanol (10 mL) A solution of 0.338 g (0.6 mmol) of ligand L in dichloromethane (10 mL). 15 It was slowly added dropwise to the solution. The color of the solution immediately changed to deep red, and a large amount of precipitate was formed. The reaction was stirred at room temperature for 6 hours, and then anhydrous diethyl ether was added to induce precipitation. Filtration was performed to obtain a filter cake, the filter cake was washed with anhydrous diethyl ether, and dried under vacuum to obtain Ni 17 It was obtained as a brownish-red powder solid. Yield: 80.2%. Elemental analysis (C 72 H 104Calculated for Br8N4Ni3O2): C, 46.17; H, 5.60; N, 2.99; Experimental values ​​(%): C, 46.24; H, 5.80; N, 3.13.

[0398] Ethylene Polymerization: After continuous drying at 130 °C for 6 hours, a 1 L stainless steel polymerization autoclave equipped with mechanical stirring was emptied while hot and refilled with N2 gas three times. 500 mL of hexane was added to the polymerization autoclave, followed by the addition of 5.0 mL of methylaluminoxane (MAO) (1.53 mol / l solution in toluene) and 4.7 mg (2.5 μmol) of complex Ni 17 ethylene was added. The ethylene pressure was maintained at 10 atm, and the reaction was vigorously stirred at 60°C for 30 minutes. The reaction mixture was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain polyethylene. The results are shown in Table 3 below.

[0399] Comparative Example 7

[0400] After continuous drying at 130 °C for 6 hours, a 1 L stainless steel polymerization autoclave equipped with mechanical stirring was emptied while hot and refilled with N2 gas three times. 500 mL of hexane was added to the polymerization autoclave, followed by the addition of 5.0 mL of methylaluminoxane (MAO) (a 1.53 mol / l solution in toluene) and 4.8 mg (7.5 μmol) of catalyst compound C. The ethylene pressure was maintained at 10 atm, and the reaction was vigorously stirred at 60 °C for 30 minutes. The reaction mixture was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain polyethylene. The results are shown in Table 3 below.

[0401] Catalytic compound C

[0402] Comparative Example 8

[0403] After continuous drying at 130 °C for 6 hours, a 1 L stainless steel polymerization autoclave equipped with mechanical stirring was emptied while hot and refilled with N2 gas three times. 500 mL of hexane was added to the polymerization autoclave, followed by the addition of 5.0 mL of methylaluminoxane (MAO) (a 1.53 mol / l solution in toluene) and 4.8 mg (7.5 μmol) of catalyst compound C. The ethylene pressure was maintained at 10 atm, and the reaction was vigorously stirred at 100 °C for 30 minutes. The reaction mixture was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain polyethylene. The results are shown in Table 3 below.

[0404] Comparative Example 9

[0405] After continuous drying at 130 °C for 6 hours, a 1 L stainless steel polymerization autoclave equipped with mechanical stirring was emptied while hot and refilled with N2 gas three times. 500 mL of hexane and 10 mL of 1-hexene were added to the polymerization autoclave, followed by the addition of 5.0 mL of methylaluminoxane (MAO) (a 1.53 mol / l solution in toluene) and 4.8 mg (7.5 μmol) of catalyst compound C. The ethylene pressure was maintained at 10 atm, and the reaction was vigorously stirred at 100 °C for 30 minutes. The reaction mixture was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain the polymer. The results are shown in Table 3 below.

[0406] Comparative Example 10

[0407] After continuous drying at 130 °C for 6 hours, a 1 L stainless steel polymerization autoclave equipped with mechanical stirring was emptied while hot and refilled with N2 gas three times. 500 mL of hexane was added to the polymerization autoclave, followed by the addition of 5.0 mL of methylaluminoxane (MAO) (a 1.53 mol / l solution in toluene) and 4.7 mg (7.5 μmol) of catalyst compound D. The ethylene pressure was maintained at 10 atm, and the reaction was vigorously stirred at 90 °C for 30 minutes. The reaction mixture was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain polyethylene. The polymerization activity was 0.02 × 10⁻⁶. 6 g·mol -1 (Ni)·h -1 It was confirmed as such, and the results are shown in Table 3 below.

[0408] Catalytic compound D

[0409] Examples complex Active (10 6 g / molNi.h) Mw×10 -4 Mw / Mn Example 27 In 11 11.76 9.38 2.25 Example 28 In 11 4.14 4.32 2.21 Example 29 In 11 6.32 5.37 2.12 Example 30 In 11 17.42 12.4 2.08 Example 31 In 11 13.28 10.2 2.03 Example 32 In 12 18.32 73.4 2.02 Example 33 In 12 8.30 31.3 2.06 Example 34 In 12 9.20 32.7 2.01 Example 35 In 12 18.41 31.3 2.01 Example 36 In 12 15.42 18.7 2.04 Example 37 In 13 9.21 33.6 2.03 Example 38 In 14 5.44 3.2 2.01 Example 39 In 15 13.21 16.24 2.18 Example 40 In 16 6.03 8.96 2.09 Example 41 In 17 17.6 63.2 2.03 Comparative Example 7 C 8.49 8.02 2.62 Comparative Example 8 C 1.21 1.33 2.70 Comparative Example 9 C 1.25 1.35 2.82 Comparative Example 10 D a very small amount

[0410] In Table 3, when the metal complex of the present invention is used as the main catalyst, the metal complex of the present invention has much higher polymerization activity under high-temperature polymerization conditions compared to the complexes of Comparative Examples 7 and 8, and the obtained polymer has a significantly higher molecular weight and a narrower molecular weight distribution than the polymer obtained in the Comparative Examples.

[0411] Example 41

[0412] 1) Ligand L 16 (Represented by structural chemical formula B, where R 1 , R 3 , R 4 , and R 6 is isopropyl, and R 2 , R 5, R 7 - R 10 , R 21 , and R 22(is hydrogen) was prepared according to the literature Organometallics, 2013, 32, 2291-2299.

[0413] Chemical formula B

[0414] 2) Complex Ni 18 Preparation of (represented by structural formula IIIc, where R 1 , R 3 , R 4 , and R 6 is isopropyl, and R 2 , R 5, R 7 - R 10 , R 21 , and R 22 is hydrogen, and R 11 ≡ ethyl, M is nickel, Y is O, and X is Br):

[0415] Chemical formula IIIc

[0416] 0.277 g (0.9 mmol) of (DME)NiBr2 in ethanol (10 mL) A solution of 0.332 g (0.6 mmol) of ligand L in dichloromethane (10 mL). 16 It was slowly added dropwise to the solution. The color of the solution immediately changed to deep red, and a large amount of precipitate was formed. The reaction was stirred at room temperature for 6 hours, followed by the addition of anhydrous diethyl ether to induce precipitation. Filtration was performed to obtain a filter cake, which was washed with anhydrous diethyl ether and dried under vacuum to obtain Ni8 as a red powder solid. Yield: 78.2%. Elemental analysis (C 84 H 98 Calculated for Br6N4Ni3O2): C, 54.50; H, 5.34; N, 3.03; Experimental values ​​(%): C, 54.38; H, 5.72; N, 3.16.

[0417] 3) Ethylene polymerization:

[0418] After continuous drying at 130 °C for 6 hours, a 1 L stainless steel polymerization autoclave equipped with mechanical stirring was emptied while hot and refilled with N2 gas three times. 500 mL of hexane was added to the polymerization autoclave, followed by the addition of 5.0 mL of methylaluminoxane (MAO) (1.53 mol / l solution in toluene) and 4.6 mg (2.5 μmol) of complex Ni 18 Ethylene was added. The ethylene pressure was maintained at 10 atm, and the reaction was vigorously stirred at 60°C for 30 minutes. The reaction mixture was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain polyethylene. The results are shown in Table 4 below.

[0419] Example 42

[0420] Ethylene polymerization was carried out according to the procedure for ethylene polymerization described in Example 41, except that the ethylene polymerization temperature was 100°C. The results are shown in Table 4 below.

[0421] Example 43

[0422] After continuous drying at 130 °C for 6 hours, a 1 L stainless steel polymerization autoclave equipped with mechanical stirring was emptied while hot and refilled with N2 gas three times. 500 mL of hexane and 10 mL of 1-hexene were added to the polymerization autoclave, followed by the addition of 5.0 mL of methylaluminoxane (MAO) (1.53 mol / l solution in toluene) and 4.6 mg (2.5 μmol) of complex Ni 18 Ethylene was added. The ethylene pressure was maintained at 10 atm, and the reaction was vigorously stirred at 100°C for 30 minutes. The reaction mixture was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain a polymer. The results are shown in Table 4 below.

[0423] Example 44

[0424] After continuous drying at 130 °C for 6 hours, a 1 L stainless steel polymerization autoclave equipped with mechanical stirring was emptied while hot and refilled with N2 gas three times. 500 mL of hexane was added to the polymerization autoclave, and simultaneously, 4.6 mg (2.5 μmol) of the complex Ni 18 6 mL of 10-undecen-1-ol, 30 mL of AlEt3 (1.0 mol / L solution in hexane), and 5.0 mL of MAO (1.53 mol / L solution in toluene) were added to this. The ethylene pressure was maintained at 10 atm, and the reaction was stirred at 60 °C for 30 minutes. The reaction mixture was finally neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain the polymer. The results are shown in Table 4 below.

[0425] Example 44A

[0426] Copolymerization of ethylene and 10-undecen-1-ol was carried out according to the polymerization procedure described in Example 44, except that the polymerization temperature was 100°C. The results are shown in Table 4 below.

[0427] Example 45

[0428] After continuous drying at 130 °C for 6 hours, a 1 L stainless steel polymerization autoclave equipped with mechanical stirring was emptied while hot and refilled with N2 gas three times. 500 mL of hexane was added to the polymerization autoclave, and simultaneously, 4.6 mg (2.5 μmol) of the complex Ni 18 5.52 g of 10-undecenatenic acid, 30 mL of AlEt3 (1.0 mol / L solution in hexane), and 5.0 mL of MAO (1.53 mol / L solution in toluene) were added to this. The ethylene pressure was maintained at 10 atm, and the reaction was stirred at 60 °C for 30 minutes. The reaction mixture was finally neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain the polymer. The results are shown in Table 4 below.

[0429] Example 45A

[0430] Copolymerization of ethylene and 10-undecenatenic acid was carried out according to the polymerization procedure described in Example 45, except that the polymerization temperature was 100°C. The results are shown in Table 4 below.

[0431] Example 46

[0432] 1) Ligand L 17 (Represented by structural chemical formula B, where R 1 , R 3 , R 4 and R 6 is ethyl, and R 2 , R 5, R 7 -R 10 and R 22 is hydrogen, and R 21 (It is tert-butyl) was prepared according to patent CN106397264.

[0433] 2) Complex Ni 19 Preparation of (represented by structural formula IIIc, where R 1 , R 3 , R 4 and R 6 is ethyl, and R 2 , R 5 , R 7 - R 10 and R 22 is hydrogen, and R 21 is tert-butyl, and R 11 ≡ ethyl, M is nickel, Y is O, and X is Br):

[0434] 0.277 g (0.9 mmol) of (DME)NiBr2 in ethanol (10 mL) A solution of 0.365 g (0.6 mmol) of ligand L in dichloromethane (10 mL). 17It was slowly added dropwise to the solution. The color of the solution immediately changed to deep red, and a large amount of precipitate was formed. The reaction was stirred at room temperature for 6 hours, and then anhydrous diethyl ether was added to induce precipitation. Filtration was performed to obtain a filter cake, the filter cake was washed with anhydrous diethyl ether, and dried under vacuum to obtain Ni 19 was obtained as a brownish-red powder solid. Yield: 82.0%. Elemental analysis (C 92 H 114 Calculated for Br6N4Ni3O2): C, 56.28; H, 5.85; N, 2.85; Experimental values ​​(%): C, 56.43; H, 6.12; N, 3.08.

[0435] 3) Ethylene polymerization:

[0436] After continuous drying at 130 °C for 6 hours, a 1 L stainless steel polymerization autoclave equipped with mechanical stirring was emptied while hot and refilled with N2 gas three times. 500 mL of hexane was added to the polymerization autoclave, followed by the addition of 5.0 mL of methylaluminoxane (MAO) (1.53 mol / l solution in toluene) and 4.9 mg (2.5 μmol) of complex Ni 19 ...was added. The ethylene pressure was maintained at 10 atm, and the reaction was vigorously stirred at 60°C for 30 minutes. The reaction mixture was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain polyethylene. The results are shown in Table 4 below.

[0437] Example 47

[0438] Ethylene polymerization was carried out according to the procedure for ethylene polymerization described in Example 46, except that the ethylene polymerization temperature was 100°C. The results are shown in Table 4 below.

[0439] Example 48

[0440] After continuous drying at 130 °C for 6 hours, a 1 L stainless steel polymerization autoclave equipped with mechanical stirring was emptied while hot and refilled with N2 gas three times. 500 mL of hexane and 10 mL of 1-hexene were added to the polymerization autoclave, followed by the addition of 5.0 mL of methylaluminoxane (MAO) (1.53 mol / l solution in toluene) and 4.9 mg (2.5 μmol) of complex Ni 19 ...was added. The ethylene pressure was maintained at 10 atm, and the reaction was vigorously stirred at 100°C for 30 minutes. The reaction mixture was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain a polymer. The results are shown in Table 4 below.

[0441] Example 49

[0442] After continuous drying at 130 °C for 6 hours, a 1 L stainless steel polymerization autoclave equipped with mechanical stirring was emptied while hot and refilled with N2 gas three times. 500 mL of hexane was added to the polymerization autoclave, and simultaneously, 4.9 mg (2.5 μmol) of the complex Ni 19 6 mL of 10-undecen-1-ol, 30 mL of AlEt3 (1.0 mol / L solution in hexane), and 5.0 mL of MAO (1.53 mol / L solution in toluene) were added to this. The ethylene pressure was maintained at 10 atm, and the reaction was stirred at 60 °C for 30 minutes. The reaction mixture was finally neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain the polymer. The results are shown in Table 4 below.

[0443] Example 49A

[0444] Copolymerization of ethylene and 10-undecen-1-ol was carried out according to the polymerization procedure described in Example 49, except that the polymerization temperature was 100°C. The results are shown in Table 4 below.

[0445] Example 50

[0446] After continuous drying at 130 °C for 6 hours, a 1 L stainless steel polymerization autoclave equipped with mechanical stirring was emptied while hot and refilled with N2 gas three times. 500 mL of hexane was added to the polymerization autoclave, and simultaneously, 4.9 mg (2.5 μmol) of the complex Ni 19 5.52 g of 10-undecenatenic acid, 30 mL of AlEt3 (1.0 mol / L solution in hexane), and 5.0 mL of MAO (1.53 mol / L solution in toluene) were added to this. The ethylene pressure was maintained at 10 atm, and the reaction was stirred at 60 °C for 30 minutes. The reaction mixture was finally neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain the polymer. The results are shown in Table 4 below.

[0447] Example 50A

[0448] Copolymerization of ethylene and 10-undecenatenic acid was carried out according to the polymerization procedure described in Example 50, except that the polymerization temperature was 100°C. The results are shown in Table 4 below.

[0449] Example 51

[0450] 1) Ligand L 18 Manufacture of:

[0451] Compound A: (1.77 g, 5.1 mmol) and 2,6-dimethyl-4-bromo-aniline (2.3 g, 11.3 mmol) were refluxed in 100 mL of toluene for 1 day in the presence of p-toluenesulfonic acid (0.02 g) as a catalyst. The solvent was removed by filtration, the residue was dissolved in dichloromethane, and separated by column chromatography using petroleum ether / ethyl acetate as the eluent to obtain a yellow solid. Yield: 78%. 1H NMR (CDCl3, δ, ppm): 1.84 (s, 12H), 1.19 ppm (s, 18H), 4.70 (s, 2H), 7.04 (8H), 7.12 (s, 2H).

[0452] 2) Complex Ni 20 Preparation of (represented by structural formula IIIc, where R 1 , R 3 , R 4 and R 6 is methyl, and R 2 and R 5 is bromine, and R 7 -R 10 and R 22 is hydrogen, and R 21 is tert-butyl, and R 11 ≡ ethyl, M is nickel, Y is O, and X is Br):

[0453] 0.277 g (0.9 mmol) of (DME)NiBr2 in ethanol (10 mL) A solution of 0.426 g (0.6 mmol) of ligand L in dichloromethane (10 mL). 18 It was slowly added dropwise to the solution. The color of the solution immediately changed to deep red, and a large amount of precipitate was formed. The reaction was stirred at room temperature for 6 hours, and then anhydrous diethyl ether was added to induce precipitation. Filtration was performed to obtain a filter cake, the filter cake was washed with anhydrous diethyl ether, and dried under vacuum to obtain Ni 20 It was obtained as a brownish-red powder solid. Yield: 82.0%. Elemental analysis (C 84 H 94 Br 10 Calculated for N4Ni3O2): C, 46.56; H, 4.37; N, 2.59; Experimental values ​​(%): C, 46.43; H, 4.72; N, 2.98.

[0454] 3) Ethylene polymerization:

[0455] After continuous drying at 130 °C for 6 hours, a 1 L stainless steel polymerization autoclave equipped with mechanical stirring was emptied while hot and refilled with N2 gas three times. 500 mL of hexane was added to the polymerization autoclave, followed by the addition of 5.0 mL of methylaluminoxane (MAO) (1.53 mol / l solution in toluene) and 5.4 mg (2.5 μmol) of complex Ni 20 Ethylene was added. The ethylene pressure was maintained at 10 atm, and the reaction was vigorously stirred at 100°C for 30 minutes. The reaction mixture was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain polyethylene. The results are shown in Table 4 below.

[0456] Example 52

[0457] 1) Complex Ni 21 Preparation of (represented by structural formula IIIc, where R 1 , R 3 , R 4 and R 6 is ethyl, and R 2 , R 5 , R 7 -R 10 and R 22 is hydrogen, and R 21 is tert-butyl, and R 11 ≡ is isobutyl, M is nickel, Y is O, and X is Br):

[0458] 0.277 g (0.9 mmol) of (DME)NiBr2 in 2-methyl-1-propanol (10 mL) A solution of 0.365 g (0.6 mmol) of ligand L in dichloromethane (10 mL). 17It was slowly added dropwise to the solution. The color of the solution immediately changed to deep red, and a large amount of precipitate was formed. The reaction was stirred at room temperature for 6 hours, and then anhydrous diethyl ether was added to induce precipitation. Filtration was performed to obtain a filter cake, the filter cake was washed with anhydrous diethyl ether, and dried under vacuum to obtain Ni 21 It was obtained as a brownish-red powder solid. Yield: 83.0%. Elemental analysis (C 96 H 122 Calculated for Br6N4Ni3O2): C, 57.09; H, 6.09; N, 2.77; Experimental values ​​(%): C, 57.24; H, 6.32; N, 3.04.

[0459] 3) Ethylene polymerization:

[0460] After continuous drying at 130 °C for 6 hours, a 1 L stainless steel polymerization autoclave equipped with mechanical stirring was emptied while hot and refilled with N2 gas three times. 500 mL of hexane was added to the polymerization autoclave, followed by the addition of 5.0 mL of methylaluminoxane (MAO) (1.53 mol / l solution in toluene) and 5.0 mg (2.5 μmol) of complex Ni 21 Ethylene was added. The ethylene pressure was maintained at 10 atm, and the reaction was vigorously stirred at 60°C for 30 minutes. The reaction mixture was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain polyethylene. The results are shown in Table 4 below.

[0461] Example 53

[0462] Compound B

[0463] 1) Ligand L 19 Compound B was prepared using a raw material according to the method described in patent application CN201510462932.2.

[0464] 2) Complex Ni 22 Preparation of (represented by structural chemical formula IIIc', where R 1 =R 3 =R 4 =R 6 =Et, R 2 = R 5 = R 7 -R 10 = R 31 =R 32 =H, R 11 =Et, M=Ni, Y=O, and X=Br):

[0465] Chemical formula IIIc'

[0466] 0.277 g (0.9 mmol) of (DME)NiBr2 in ethanol (10 mL) A solution of 0.358 g (0.6 mmol) of ligand L in dichloromethane (10 mL). 19 It was slowly added dropwise to the solution. The color of the solution immediately changed to deep red, and a large amount of precipitate was formed. The reaction was stirred at room temperature for 6 hours, and then anhydrous diethyl ether was added to induce precipitation. Filtration was performed to obtain a filter cake, the filter cake was washed with anhydrous diethyl ether, and dried under vacuum to obtain Ni 22 was obtained as a brownish-red powder solid. Yield: 84.3%. Elemental analysis (C 92 H 90 Calculated for Br6N4Ni3O2): C, 56.98; H, 4.68; N, 2.89; Experimental values ​​(%): C, 56.78; H, 4.62; N, 3.18.

[0467] 3) Ethylene polymerization:

[0468] After continuous drying at 130 °C for 6 hours, a 1 L stainless steel polymerization autoclave equipped with mechanical stirring was emptied while hot and refilled with N2 gas three times. 500 mL of hexane was added to the polymerization autoclave, followed by the addition of 5.0 mL of methylaluminoxane (MAO) (1.53 mol / l solution in toluene) and 4.8 mg (2.5 μmol) of complex Ni 22 ...was added. The ethylene pressure was maintained at 10 atm, and the reaction was vigorously stirred at 60°C for 30 minutes. The reaction mixture was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain polyethylene. The results are shown in Table 4 below.

[0469] Example 54

[0470] Ethylene polymerization was carried out according to the procedure for ethylene polymerization described in Example 53, except that the ethylene polymerization temperature was 100°C. The results are shown in Table 4 below.

[0471] Comparative Example 11

[0472] Comparative catalyst E was prepared according to Organometallics, 2013, 32, 2291-2299.

[0473] Ethylene polymerization: After continuous drying at 130 °C for 6 hours, a 1 L stainless steel polymerization autoclave equipped with mechanical stirring was emptied while hot and refilled with N2 gas three times. 500 mL of hexane was added to the polymerization autoclave, followed by the addition of 5.0 mL of methylaluminoxane (MAO) (a 1.53 mol / l solution in toluene) and 5.8 mg (7.5 μmol) of comparative catalyst A. The ethylene pressure was maintained at 10 atm, and the reaction was vigorously stirred at 60 °C for 30 minutes. The reaction mixture was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain polyethylene. The results are shown in Table 4 below.

[0474] Comparative catalyst E

[0475] Comparative Example 12

[0476] Ethylene polymerization was carried out according to the procedure for ethylene polymerization described in Comparative Example 11, except that the ethylene polymerization temperature was 100°C. The results are shown in Table 4 below.

[0477] Comparative Example 13

[0478] After continuous drying at 130 °C for 6 hours, a 1 L stainless steel polymerization autoclave equipped with mechanical stirring was emptied while hot and refilled with N2 gas three times. 500 mL of hexane and 10 mL of 1-hexene were added to the polymerization autoclave, followed by the addition of 5.0 mL of methylaluminoxane (MAO) (a 1.53 mol / l solution in toluene) and 5.8 mg (7.5 μmol) of comparative catalyst E. The ethylene pressure was maintained at 10 atm, and the reaction was vigorously stirred at 100 °C for 30 minutes. The reaction mixture was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain the polymer. The results are shown in Table 4 below.

[0479] Comparative Example 4

[0480] Comparative catalyst F was prepared according to the literature J. Am. Chem. Soc, 1995, 117, 6414-6415.

[0481] After continuous drying at 130 °C for 6 hours, a 1 L stainless steel polymerization autoclave equipped with mechanical stirring was emptied while hot and refilled with N2 gas three times. 500 mL of hexane was added to the polymerization autoclave, followed by the addition of 5.0 mL of methylaluminoxane (MAO) (a 1.53 mol / l solution in toluene) and 4.7 mg (7.5 μmol) of comparative catalyst F. The ethylene pressure was maintained at 10 atm, and the reaction was vigorously stirred at 90 °C for 30 minutes. The reaction mixture was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain polyethylene. The results are shown in Table 4 below.

[0482] Comparative catalyst F

[0483] Examples complex Active (10 6 g / molNi.h) Mw×10 -4 Mw / Mn Example 41 In 18 2.12 128.0 2.31 Example 42 In 18 4.24 69.1 2.51 Example 43 In 18 4.84 70.2 2.32 Example 44 In 18 5.73 46.2 2.02 Example 44A In 18 1.27 13.22 2.01 Example 45 In 18 4.64 27.60 2.01 Example 45A In 18 1.04 12.17 2.01 Example 46 In 19 2.03 72.4 2.56 Example 47 In 19 3.26 28.4 2.86 Example 48 In 19 3.72 29.1 2.71 Example 49 In 19 2.52 22.7 2.16 Example 49A In 19 1.02 10.4 2.13 Example 50 In 19 3.26 8.7 2.14 Example 50A In 19 1.13 5.3 2.13 Example 51 In 20 2.53 4.64 2.87 Example 52 In 21 1.96 53.2 2.63 Example 53 In 22 2.58 10.37 2.42 Example 54 In 22 4.17 5.26 2.20 Comparative Example 11 E 1.58 110 2.81 Comparative Example 12 E 3.45 54.5 2.79 Comparative Example 13 E 3.62 60.8 2.58 Comparative Example 14 F 0.02 0.68 2.14

[0484] In Table 4, when the metal complex of the present invention is used as the main catalyst, the metal complex of the present invention has higher polymerization activity under high-temperature polymerization conditions compared to comparative catalysts E and F, and the obtained polymer has a higher molecular weight and a narrower molecular weight distribution than the polymer obtained in the comparative example.

[0485] The foregoing is merely a preferred embodiment of the present invention and is not intended to limit the invention. All modifications, equivalent substitutions, changes, etc. made within the spirit and principles of the present invention will be included within the scope of protection of the present invention.

Claims

Claim 1 Diimine-metal complex represented by the following chemical formula I: Formula I In the above Formula I, R1 and R2 are independently selected from the group consisting of C1-C20 alkyls having or not having substituent Q and C6-C20 aryls having or not having substituent Q, and at least one of R1 and R2 is a group represented by the following Formula A: Chemical Formula A In the above chemical formula A, R 1 -R 5 Each is independently selected from the group consisting of hydrogen, halogen, hydroxyl, C1-C20 alkyl having or not having substituent Q, C2-C20 alkenyl having or not having substituent Q, C2-C20 alkynyl having or not having substituent Q, C1-C20 alkoxy having or not having substituent Q, C2-C20 alkenoxy having or not having substituent Q, C2-C20 alkynoxy having or not having substituent Q, C6-C20 aryl having or not having substituent Q, C6-C20 aryloxy having or not having substituent Q, C7-C20 aralkyl having or not having substituent Q, C7-C20 aralkoxy having or not having substituent Q, C7-C20 alkaryl having or not having substituent Q, and C7-C20 alkaryloxy having or not having substituent Q, and R 1 -R 5 are optionally connected to form a ring or ring system; R3 and R4 are each independently hydrogen, halogen, hydroxyl, C1-C20 alkyl having or not having substituent Q, C2-C20 alkenyl having or not having substituent Q, C2-C20 alkynyl having or not having substituent Q, C1-C20 alkoxy having or not having substituent Q, C2-C20 alkenoxy having or not having substituent Q, C2-C20 alkynoxy having or not having substituent Q, C6-C20 aryl having or not having substituent Q, C6-C20 aryloxy having or not having substituent Q, C7-C20 aralkyl having or not having substituent Q, C7-C20 aralkoxy having or not having substituent Q, C7-C20 alkalil having or not having substituent Q, and C7-C20 having or not having substituent Q Selected from the group consisting of alcaryloxy, adjacent R3 and R4 groups are optionally connected to form a ring or ring system; each R 11 is independently a C1-C20 hydrocarbyl having or not having substituent Q; each Y is independently selected from the group consisting of O and S; each M is independently selected from the group consisting of nickel and palladium; each X is independently a halogen; and substituent Q is selected from the group consisting of halogen, hydroxy, C1-C10 alkyl, halogenated C1-C10 alkyl, C1-C10 alkoxy, and halogenated C1-C10 alkoxy. Claim 2 In claim 1, a dimine-metal complex having at least one of the following features: - in formula A, R 1 -R 5 Each independently hydrogen, halogen, hydroxy, C1-C10 alkyl having or not having substituent Q, C2-C10 alkenyl having or not having substituent Q, C2-C10 alkynyl having or not having substituent Q, C3-C10 cycloalkyl having or not having substituent Q, C1-C10 alkoxy having or not having substituent Q, C2-C10 alkenoxy having or not having substituent Q, C2-C10 alkynoxy having or not having substituent Q, C3-C10 cycloalkoxy having or not having substituent Q, C6-C15 aryl having or not having substituent Q, C6-C15 aryloxy having or not having substituent Q, C7-C15 aralkyl having or not having substituent Q, C7-C15 aralkoxy having or not having substituent Q, and having or not having substituent Q Selected from the group consisting of C7-C15 alkalil and C7-C15 alkaliloxy having or not having substituent Q;- each R 11 is independently a C1-C20 alkyl having or not having substituent Q, or a C1-C10 alkyl having or not having substituent Q, or a C1-C6 alkyl having or not having substituent Q; - R3 and R4 are each independently hydrogen, halogen, hydroxyl, a C1-C10 alkyl having or not having substituent Q, a C2-C10 alkenyl having or not having substituent Q, a C2-C10 alkynyl having or not having substituent Q, a C3-C10 cycloalkyl having or not having substituent Q, a C1-C10 alkoxy having or not having substituent Q, a C2-C10 alkenoxy having or not having substituent Q, a C2-C10 alkinoxy having or not having substituent Q, a C3-C10 cycloalkoxy having or not having substituent Q, a C6-C15 aryl having or not having substituent Q, or Selected from the group consisting of C6-C15 aryloxy without substituent Q, C7-C15 aralkyl having or without substituent Q, C7-C15 aralkoxy having or without substituent Q, C7-C15 alkaryl having or without substituent Q, and C7-C15 alkaryloxy having or without substituent Q; or R3 and R4 are each independently selected from the group consisting of hydrogen, C1-C10 alkyl, halogenated C1-C10 alkyl, C1-C10 alkoxy, halogenated C1-C10 alkoxy, and halogen, or selected from the group consisting of hydrogen, C1-C6 alkyl, halogenated C1-C6 alkyl, C1-C6 alkoxy, halogenated C1-C6 alkoxy, and halogen; and- Substituent Q is selected from the group consisting of halogen, hydroxy, C1-C6 alkyl, halogenated C1-C6 alkyl, C1-C6 alkoxy, and halogenated C1-C6 alkoxy. Claim 3 In claim 1, the dimine-metal complex is a dimine-metal complex represented by the following chemical formula III: Chemical Formula III In the above Chemical Formula III, R 1 -R 5 Each is independently selected from the group consisting of hydrogen, halogen, hydroxy, C1-C10 alkyl having or not having substituent Q, C3-C10 cycloalkyl having or not having substituent Q, C1-C10 alkoxy having or not having substituent Q, C3-C10 cycloalkoxy having or not having substituent Q, C6-C15 aryl having or not having substituent Q, C7-C15 aralkyl having or not having substituent Q, and C7-C15 alkaryl having or not having substituent Q; R3 and R4 are each independently selected from the group consisting of hydrogen, C1-C10 alkyl, halogenated C1-C10 alkyl, C1-C10 alkoxy, halogenated C1-C10 alkoxy, and halogen, or hydrogen, C1-C6 alkyl, halogenated C1-C6 alkyl, C1-C6 alkoxy, Selected from the group consisting of halogenated C1-C6 alkoxy and halogens; each M is nickel; each Y is O; each X is independently selected from the group consisting of fluorine, chlorine, and bromine; each R 11 is independently a C1-C20 alkyl having or not having substituent Q, or a C1-C10 alkyl having or not having substituent Q, or a C1-C6 alkyl having or not having substituent Q; substituent Q is independently selected from the group consisting of halogen, hydroxy, C1-C6 alkyl, halogenated C1-C6 alkyl, C1-C6 alkoxy, and halogenated C1-C6 alkoxy. Claim 4 In claim 1, the dimine-metal complex is a dimine-metal complex represented by the following chemical formula Ia: Formula Ia In the above formula Ia, R5-R7 are each independently selected from the group consisting of hydrogen, halogen, hydroxyl, and C1-C20 hydrocarbyl having or not having substituent Q, and R5-R7 are optionally connected to form a ring or ring system; R1, R2, R 11 , Y, M and X are as defined in Paragraph 1. Claim 5 In claim 4, a dimine-metal complex having at least one of the following features: - in formula A, R 1 -R 5 Each independently hydrogen, halogen, hydroxy, C1-C10 alkyl having or not having substituent Q, C2-C10 alkenyl having or not having substituent Q, C2-C10 alkynyl having or not having substituent Q, C3-C10 cycloalkyl having or not having substituent Q, C1-C10 alkoxy having or not having substituent Q, C2-C10 alkenoxy having or not having substituent Q, C2-C10 alkynoxy having or not having substituent Q, C3-C10 cycloalkoxy having or not having substituent Q, C6-C15 aryl having or not having substituent Q, C6-C15 aryloxy having or not having substituent Q, C7-C15 aralkyl having or not having substituent Q, C7-C15 aralkoxy having or not having substituent Q, and having or not having substituent Q Selected from the group consisting of C7-C15 alkalil and C7-C15 alkaliloxy having or not having substituent Q;- each R 11 is independently a C1-C20 alkyl having or not having substituent Q, or a C1-C10 alkyl having or not having substituent Q, or a C1-C6 alkyl having or not having substituent Q; and- substituent Q is selected from the group consisting of halogen, hydroxy, C1-C6 alkyl, halogenated C1-C6 alkyl, C1-C6 alkoxy, and halogenated C1-C6 alkoxy. Claim 6 In paragraph 4, the above dimine-metal complex is a dimine-metal complex represented by the following chemical formula IIa: Chemical Formula IIa In the above Chemical Formula IIa, R5-R 10 Each is independently selected from the group consisting of hydrogen, halogen, hydroxyl, C1-C20 alkyl having or not having substituent Q, C2-C20 alkenyl having or not having substituent Q, C2-C20 alkynyl having or not having substituent Q, C1-C20 alkoxy having or not having substituent Q, C2-C20 alkenoxy having or not having substituent Q, C2-C20 alkynoxy having or not having substituent Q, C6-C20 aryl having or not having substituent Q, C6-C20 aryloxy having or not having substituent Q, C7-C20 aralkyl having or not having substituent Q, C7-C20 aralkoxy having or not having substituent Q, C7-C20 alkaryl having or not having substituent Q, and C7-C20 alkaryloxy having or not having substituent Q, and R1, R2, M, X, Y, and R 11 is as defined in Paragraph 4. Claim 7 In claim 4, in chemical formula Ia, R5-R7 are each independently hydrogen, halogen, hydroxyl, C1-C10 alkyl having or not having substituent Q, C2-C10 alkenyl having or not having substituent Q, C2-C10 alkynyl having or not having substituent Q, C3-C10 cycloalkyl having or not having substituent Q, C1-C10 alkoxy having or not having substituent Q, C2-C10 alkenoxy having or not having substituent Q, C2-C10 alkynoxy having or not having substituent Q, C3-C10 cycloalkoxy having or not having substituent Q, C6-C15 aryl having or not having substituent Q, C6-C15 aryloxy having or not having substituent Q, C7-C15 aralkyl having or not having substituent Q, C7-C15 having or not having substituent Q A diimine-metal complex, wherein R5-R7 of formula Ia are each independently selected from the group consisting of aralkoxy, C7-C15 alkaryls having or not having substituent Q, and C7-C15 alkaryloxy having or not having substituent Q; or R5-R7 of formula Ia are each independently selected from the group consisting of hydrogen, C1-C10 alkyl, halogenated C1-C10 alkyl, C1-C10 alkoxy, halogenated C1-C10 alkoxy, and halogen, or selected from the group consisting of hydrogen, C1-C6 alkyl, halogenated C1-C6 alkyl, C1-C6 alkoxy, halogenated C1-C6 alkoxy, and halogen. Claim 8 In paragraph 6, R5-R in chemical formula IIa 10 Each is independently hydrogen, halogen, hydroxyl, C1-C10 alkyl having or not having substituent Q, C2-C10 alkenyl having or not having substituent Q, C2-C10 alkynyl having or not having substituent Q, C3-C10 cycloalkyl having or not having substituent Q, C1-C10 alkoxy having or not having substituent Q, C2-C10 alkenoxy having or not having substituent Q, C2-C10 alkynoxy having or not having substituent Q, C3-C10 cycloalkoxy having or not having substituent Q, C6-C15 aryl having or not having substituent Q, C6-C15 aryloxy having or not having substituent Q, C7-C15 aralkyl having or not having substituent Q, C7-C15 aralkoxy having or not having substituent Q, and having or not having substituent Q Selected from the group consisting of C7-C15 alkalil and C7-C15 alkaliloxy having or not having substituent Q; or R5-R of formula IIa 10 A diimine-metal complex, each independently selected from the group consisting of hydrogen, C1-C10 alkyl, halogenated C1-C10 alkyl, C1-C10 alkoxy, halogenated C1-C10 alkoxy, and halogen, or selected from the group consisting of hydrogen, C1-C6 alkyl, halogenated C1-C6 alkyl, C1-C6 alkoxy, halogenated C1-C6 alkoxy, and halogen. Claim 9 In paragraph 4, the above dimine-metal complex is represented by the following chemical formula IIIa or: Chemical Formula IIIa In the above Chemical Formula IIIa, R 1 -R 5 Each is independently selected from the group consisting of hydrogen, a halogen, a C1-C6 alkyl having or not having substituent Q, and a C1-C6 alkoxy having or not having substituent Q; R5-R 10 Each is independently selected from the group consisting of hydrogen, halogen, C1-C6 alkyl, and C1-C6 alkoxy; each M is nickel; each Y is O; each X is independently a halogen; and each R 11 is independently a C1-C6 alkyl having or not having substituent Q; or, the diimine-metal complex is 1) a complex represented by formula IIIa, where R 1 =R 3 =isopropyl, R 2 =R 4 =R 5 =R5-R 10 =H, R 11 =methyl, M=Ni, Y=O, X=Br;2) A complex represented by the chemical formula IIIa, where R 1 =R 3 =ethyl, R 2 =R 4 =R 5 =R5-R 10 =H, R 11 =methyl, M=Ni, Y=O, X=Br;3) A complex represented by the chemical formula IIIa, where R 1 =R 3 =methyl, R 2 =R 4 =R 5 =R5-R 10 =H, R 11 =methyl, M=Ni, Y=O, X=Br;4) A complex represented by the chemical formula IIIa, where R 1 -R 3 =methyl, R 4 =R 5 =R5-R 10 =H, R 11 =methyl, M=Ni, Y=O, X=Br; 5) A complex represented by the chemical formula IIIa, where R 1 =R 3 =methyl, R 2 =Br, R 4 =R 5 =R5-R 10 =H, R 11 =methyl, M=Ni, Y=O, X=Br;6) A complex represented by the chemical formula IIIa, where R 1 =R 3 =Br, R 2 =R 4 =R 5 =R5-R 10 =H, R 11 =methyl, M=Ni, Y=O, X=Br;7) A complex represented by the chemical formula IIIa, where R 1 =R 3 =Cl, R 2 =R 4 =R 5 =R5-R 10 =H, R 11 =methyl, M=Ni, Y=O, X=Br;8) A complex represented by the chemical formula IIIa, where R 1 =R 3 =F, R 2 =R 4 =R 5 =R5-R 10 =H, R 11 =methyl, M=Ni, Y=O, X=Br;9) A complex represented by the chemical formula IIIa, where R 1 =R 3 =isopropyl, R 2 =R 4 =R 5 =R5-R 10 =H, R 11 =ethyl, M=Ni, Y=O, X=Br;10) A complex represented by the chemical formula IIIa, where R 1 =R 3 =ethyl, R 2 =R 4 =R 5 =R5-R 10 =H, R 11 =ethyl, M=Ni, Y=O, X=Br;11) A complex represented by the chemical formula IIIa, where R 1 =R 3 =methyl, R 2 =R 4 =R 5 =R5-R 10 =H, R 11 =ethyl, M=Ni, Y=O, X=Br;12) A complex represented by the chemical formula IIIa, where R 1 -R 3 =methyl, R 4 =R 5 =R5-R 10 =H, R 11 =ethyl, M=Ni, Y=O, X=Br;13) A complex represented by the chemical formula IIIa, where R 1 =R 3 =methyl, R 2 =Br, R 4 =R 5 =R5-R 10 =H, R 11 =ethyl, M=Ni, Y=O, X=Br;14) A complex represented by the chemical formula IIIa, where R 1 =R 3 =Br, R 2 =R 4 =R 5 =R5-R 10 =H, R 11 =ethyl, M=Ni, Y=O, X=Br;15) A complex represented by the chemical formula IIIa, where R 1 =R 3 =Cl, R 2 =R 4 =R 5 =R5-R 10 =H, R 11 =ethyl, M=Ni, Y=O, X=Br;16) A complex represented by the chemical formula IIIa, where R 1 =R 3 =F, R 2 =R 4 =R 5 =R5-R 10 =H, R 11 =ethyl, M=Ni, Y=O, X=Br;17) A complex represented by the chemical formula IIIa, where R 1 =R 3 =isopropyl, R 2 =R 4 =R 5 =R5-R 10 =H, R 11 =isobutyl, M=Ni, Y=O, X=Br;18) Complex represented by chemical formula IIIa, where R 1 =R 3 =ethyl, R 2 =R 4 =R 5 =R5-R 10 =H, R 11 =isobutyl, M=Ni, Y=O, X=Br;19) A complex represented by the chemical formula IIIa, where R 1 =R 3 =methyl, R 2 =R 4 =R 5 =R5-R 10 =H, R 11 =isobutyl, M=Ni, Y=O, X=Br;20) Complex represented by chemical formula IIIa, where R 1 - R 3 =methyl, R 4 =R 5 =R5-R 10 =H, R 11 =isobutyl, M=Ni, Y=O, X=Br;21) A complex represented by the chemical formula IIIa, where R 1 =R 3 =methyl, R 2 =Br, R 4 =R 5 =R5-R 10 =H, R 11 =isobutyl, M=Ni, Y=O, X=Br;22) Complex represented by chemical formula IIIa, where R 1 =R 3 =Br, R 2 =R 4 =R 5 =R5-R 10 =H, R 11 =isobutyl, M=Ni, Y=O, X=Br;23) Complex represented by chemical formula IIIa, where R 1 =R 3 =Cl, R 2 =R 4 =R 5 =R5-R 10 =H, R 11 =isobutyl, M=Ni, Y=O, X=Br;24) A complex represented by the chemical formula IIIa, where R 1 =R 3 =F, R 2 =R 4 =R 5 =R5-R 10 =H, R 11 =isobutyl, M=Ni, Y=O, X=Br;25) A complex represented by the chemical formula IIIa, where R 1 =R 3 =isopropyl, R 2 =R 4 =R 5 =R5=R6=R9=R 10 =H, R7=R8=methyl, R 11 =ethyl, M=Ni, Y=O, X=Br;26) A complex represented by the chemical formula IIIa, where R 1 =R 3 =ethyl, R 2 =R 4 =R 5 =R5=R6=R9=R 10 =H, R7=R8=methyl, R 11 =ethyl, M=Ni, Y=O, X=Br;27) A complex represented by the chemical formula IIIa, where R 1 =R 3 =methyl, R 2 =R 4 =R 5 =R5=R6=R9=R 10 =H, R7=R8=methyl, R 11 =ethyl, M=Ni, Y=O, X=Br;28) A complex represented by the chemical formula IIIa, where R 1 - R 3 =methyl, R 4 =R 5 =R5=R6=R9=R 10 =H, R7=R8=methyl, R 11 =ethyl, M=Ni, Y=O, X=Br;29) A complex represented by the chemical formula IIIa, where R 1 =R 3 =methyl, R 2 =Br, R 4 =R 5 =R5=R6=R9=R 10 =H, R7=R8=methyl, R 11 =ethyl, M=Ni, Y=O, X=Br;30) A complex represented by the chemical formula IIIa, where R 1 =R 3 =Br, R 2 =R 4 =R 5 =R5=R6=R9=R 10 =H, R7=R8=methyl, R 11 =ethyl, M=Ni, Y=O, X=Br;31) A complex represented by the chemical formula IIIa, where R 1 =R 3 =Cl, R 2 =R 4 =R 5 =R5=R6=R9=R 10 =H, R7=R8=methyl, R 11 =ethyl, M=Ni, Y=O, X=Br; and 32) a complex represented by the chemical formula IIIa, where R 1 =R 3 =F, R 2 =R 4 =R 5 =R5=R6=R9=R 10 =H, R7=R8=methyl, R 11 = A diimine-metal complex selected from the group consisting of ethyl, M=Ni, Y=O, and X=Br. Claim 10 In claim 1, the dimine-metal complex is a dimine-metal complex represented by the following chemical formula Ib: Formula Ib In the above formula Ib, R1 and R2 are each independently selected from the group consisting of C1-C20 alkyls having or not having substituent Q and C6-C20 aryls having or not having substituent Q, and at least one of R1 and R2 is a group represented by the following formula A: Chemical Formula A In the above chemical formula A, R 1 -R 5 Each is independently selected from the group consisting of hydrogen, halogen, hydroxyl, C1-C20 alkyl having or not having substituent Q, C2-C20 alkenyl having or not having substituent Q, C2-C20 alkynyl having or not having substituent Q, C1-C20 alkoxy having or not having substituent Q, C2-C20 alkenoxy having or not having substituent Q, C2-C20 alkynoxy having or not having substituent Q, C6-C20 aryl having or not having substituent Q, C6-C20 aryloxy having or not having substituent Q, C7-C20 aralkyl having or not having substituent Q, C7-C20 aralkoxy having or not having substituent Q, C7-C20 alkaryl having or not having substituent Q, and C7-C20 alkaryloxy having or not having substituent Q, and R 1 -R 5 are optionally connected to form a ring or ring system; R5-R8 are each independently selected from the group consisting of C1-C20 hydrocarbyl having or not having hydrogen, halogen, hydroxyl, and substituent Q, and R5-R8 are optionally connected to form a ring or ring system; and each R 12 is independently a C1-C20 hydrocarbyl with or without substituent Q; each Y is independently selected from the group consisting of O and S; each M is independently selected from the group consisting of nickel and palladium; and each X is independently a halogen. Claim 11 In claim 10, a dimine-metal complex having at least one of the following features: - in formula A, R 1 -R 5 Each independently hydrogen, halogen, hydroxy, C1-C10 alkyl having or not having substituent Q, C2-C10 alkenyl having or not having substituent Q, C2-C10 alkynyl having or not having substituent Q, C3-C10 cycloalkyl having or not having substituent Q, C1-C10 alkoxy having or not having substituent Q, C2-C10 alkenoxy having or not having substituent Q, C2-C10 alkynoxy having or not having substituent Q, C3-C10 cycloalkoxy having or not having substituent Q, C6-C15 aryl having or not having substituent Q, C6-C15 aryloxy having or not having substituent Q, C7-C15 aralkyl having or not having substituent Q, C7-C15 aralkoxy having or not having substituent Q, and having or not having substituent Q Selected from the group consisting of C7-C15 alkalil and C7-C15 alkaliloxy having or not having substituent Q;- each R 12 is independently a C1-C20 alkyl having or not having substituent Q, or a C1-C10 alkyl having or not having substituent Q, or a C1-C6 alkyl having or not having substituent Q; and- substituent Q is selected from the group consisting of halogen, hydroxy, C1-C6 alkyl, halogenated C1-C6 alkyl, C1-C6 alkoxy, and halogenated C1-C6 alkoxy. Claim 12 In claim 10, the above dimine-metal complex is a dimine-metal complex represented by the following chemical formula IIIb: Chemical Formula IIIb In the above Chemical Formula IIIb, R 1 -R 11 are each independently selected from the group consisting of hydrogen, halogen, hydroxyl, C1-C20 alkyl having or not having substituent Q, C2-C20 alkenyl having or not having substituent Q, C2-C20 alkynyl having or not having substituent Q, C1-C20 alkoxy having or not having substituent Q, C2-C20 alkenoxy having or not having substituent Q, C2-C20 alkynoxy having or not having substituent Q, C6-C20 aryl having or not having substituent Q, C6-C20 aryloxy having or not having substituent Q, C7-C20 aralkyl having or not having substituent Q, C7-C20 aralkoxy having or not having substituent Q, C7-C20 alkaryl having or not having substituent Q, and C7-C20 alkaryloxy having or not having substituent Q, and M, X, Y, and R 12 is as defined in Paragraph 10. Claim 13 In Paragraph 12, R 1 -R 11 Each is independently hydrogen, halogen, hydroxyl, C1-C10 alkyl having or not having substituent Q, C2-C10 alkenyl having or not having substituent Q, C2-C10 alkynyl having or not having substituent Q, C3-C10 cycloalkyl having or not having substituent Q, C1-C10 alkoxy having or not having substituent Q, C2-C10 alkenoxy having or not having substituent Q, C2-C10 alkynoxy having or not having substituent Q, C3-C10 cycloalkoxy having or not having substituent Q, C6-C15 aryl having or not having substituent Q, C6-C15 aryloxy having or not having substituent Q, C7-C15 aralkyl having or not having substituent Q, C7-C15 aralkoxy having or not having substituent Q, and having or not having substituent Q Selected from the group consisting of C7-C15 alkalil and C7-C15 alkaliloxy having or not having substituent Q; or R 1 -R 11 A diimine-metal complex, each independently selected from the group consisting of hydrogen, C1-C10 alkyl, halogenated C1-C10 alkyl, C1-C10 alkoxy, halogenated C1-C10 alkoxy, and halogen, or selected from the group consisting of hydrogen, C1-C6 alkyl, halogenated C1-C6 alkyl, C1-C6 alkoxy, halogenated C1-C6 alkoxy, and halogen. Claim 14 In paragraph 12, 1) a dimine-metal complex represented by the chemical formula IIIb, where R 1 =R 3 =methyl, R 2 =R 4 -R 7 =R 10 =H, R 8 =R 9 =R 11 =R 12 =methyl, M=Ni, Y=O, X=Br;2) Dimine-metal complex represented by chemical formula IIIb, where R 1 =R 3 =ethyl, R 2 =R 4 -R 7 =R 10 =H, R 8 =R 9 =R 11 =R 12 =methyl, M=Ni, Y=O, X=Br;3) Dimine-metal complex represented by chemical formula IIIb, where R 1 =R 3 =isopropyl, R 2 =R 4 -R 7 =R 10 =H, R 8 =R 9 =R 11 =R 12 =methyl, M=Ni, Y=O, X=Br;4) Dimine-metal complex represented by chemical formula IIIb, where R 1 -R 3 =methyl, R 4 -R 7 =R 10 =H, R 8 =R 9 =R 11 =R 12 =methyl, M=Ni, Y=O, X=Br;5) Dimine-metal complex represented by chemical formula IIIb, where R 1 =R 3 =methyl, R 2 =Br, R 4 -R 7 =R 10 =H, R 8 =R 9 =R 11 =R 12 =methyl, M=Ni, Y=O, X=Br;6) Dimine-metal complex represented by chemical formula IIIb, where R 1 =R 3 =F, R 2 =R 4 -R 7 =R 10 =H, R 8 =R 9 =R 11 =R 12 =methyl, M=Ni, Y=O, X=Br;7) Dimine-metal complex represented by chemical formula IIIb, where R 1 =R 3 =Cl, R 2 =R 4 -R 7 =R 10 =H, R 8 =R 9 =R 11 =R 12 =methyl, M=Ni, Y=O, X=Br;8) Dimine-metal complex represented by chemical formula IIIb, where R 1 =R 3 =Br, R 2 =R 4 -R 7 =R 10 =H, R 8 =R 9 =R 11 =R 12 =methyl, M=Ni, Y=O, X=Br;9) Dimine-metal complex represented by chemical formula IIIb, where R 1 =R 3 =methyl, R 2 =R 4 -R 7 =R 10 =H, R 8 =R 9 =R 11 =methyl, R 12 =ethyl, M=Ni, Y=O, X=Br;10) Dimine-metal complex represented by chemical formula IIIb, where R 1 =R 3 =ethyl, R 2 =R 4 -R 7 =R 10 =H, R 8 =R 9 =R 11 =methyl, R 12 =ethyl, M=Ni, Y=O, X=Br;11) Dimine-metal complex represented by chemical formula IIIb, where R 1 =R 3 =isopropyl, R 2 =R 4 -R 7 =R 10 =H, R 8 =R 9 =R 11 =methyl, R 12 =ethyl, M=Ni, Y=O, X=Br;12) Dimine-metal complex represented by chemical formula IIIb, where R 1 -R 3 =methyl, R 4 -R 7 =R 10 =H, R 8 =R 9 =R 11 =methyl, R 12 =ethyl, M=Ni, Y=O, X=Br;13) Dimine-metal complex represented by chemical formula IIIb, where R 1 =R 3 =methyl, R 2 =Br, R 4 -R 7 =R 10 =H, R 8 =R 9 =R 11 =methyl, R 12 =ethyl, M=Ni, Y=O, X=Br;14) Dimine-metal complex represented by chemical formula IIIb, where R 1 =R 3 =F, R 2 =R 4 -R 7 =R 10 =H, R 8 =R 9 =R 11 =methyl, R 12 =ethyl, M=Ni, Y=O, X=Br;15) Dimine-metal complex represented by chemical formula IIIb, where R 1 =R 3 =Cl, R 2 =R 4 -R 7 =R 10 =H, R 8 =R 9 =R 11 =methyl, R 12 =ethyl, M=Ni, Y=O, X=Br;16) Dimine-metal complex represented by chemical formula IIIb, where R 1 =R 3 =Br, R 2 =R 4 -R 7 =R 10 =H, R 8 =R 9 =R 11 =methyl, R 12 =ethyl, M=Ni, Y=O, X=Br;17) Dimine-metal complex represented by chemical formula IIIb, where R 1 =R 3 =methyl, R 2 =R 4 -R 7 =R 10 =H, R 8 =R 9 =R 11 =methyl, R 12 =isobutyl, M=Ni, Y=O, X=Br;18) Dimine-metal complex represented by chemical formula IIIb, where R 1 =R 3 =ethyl, R 2 =R 4 -R 7 =R 10 =H, R 8 =R 9 =R 11 =methyl, R 12 =isobutyl, M=Ni, Y=O, X=Br;19) Dimine-metal complex represented by chemical formula IIIb, where R 1 =R 3 =isopropyl, R 2 =R 4 -R 7 =R 10 =H, R 8 =R 9 =R 11 =methyl, R 12 =isobutyl, M=Ni, Y=O, X=Br;20) Dimine-metal complex represented by chemical formula IIIb, where R 1 -R 3 =methyl, R 4 -R 7 =R 10 =H, R 8 =R 9 =R 11 =methyl, R 12 =isobutyl, M=Ni, Y=O, X=Br;21) Dimine-metal complex represented by chemical formula IIIb, where R 1 =R 3 =methyl, R 2 =Br, R 4 -R 7 =R 10 =H, R 8 =R 9 =R 11 =methyl, R 12 =isobutyl, M=Ni, Y=O, X=Br;22) Dimine-metal complex represented by chemical formula IIIb, where R 1 =R 3 =F, R 2 =R 4 -R 7 =R 10 =H, R 8 =R 9 =R 11 =methyl, R 12 =isobutyl, M=Ni, Y=O, X=Br;23) Dimine-metal complex represented by chemical formula IIIb, where R 1 =R 3 =Cl, R 2 =R 4 -R 7 =R 10 =H, R 8 =R 9 =R 11 =methyl, R 12 =isobutyl, M=Ni, Y=O, X=Br;24) Dimine-metal complex represented by chemical formula IIIb, where R 1 =R 3 =Br, R 2 =R 4 -R 7 =R 10 =H, R 8 =R 9 =R 11 =methyl, R 12 =isobutyl, M=Ni, Y=O, X=Br;25) Dimine-metal complex represented by chemical formula IIIb, where R 1 =R 3 =methyl, R 2 =R 4 -R 7 =R 10 =H, R 8 =R 9 =methyl, R 11 =bromomethyl, R 12 =ethyl, M=Ni, Y=O, X=Br;26) Dimine-metal complex represented by chemical formula IIIb, where R 1 =R 3 =ethyl, R 2 =R 4 -R 7 =R 10 =H, R 8 =R 9 =methyl, R 11 =bromomethyl, R 12 =ethyl, M=Ni, Y=O, X=Br;27) Dimine-metal complex represented by chemical formula IIIb, where R 1 =R 3 =isopropyl, R 2 =R 4 -R 7 =R 10 =H, R 8 =R 9 =methyl, R 11 =bromomethyl, R 12 =ethyl, M=Ni, Y=O, X=Br;28) Dimine-metal complex represented by chemical formula IIIb, where R 1 -R 3 =methyl, R 4 -R 7 =R 10 =H, R 8 =R 9 =methyl, R 11 =bromomethyl, R 12 =ethyl, M=Ni, Y=O, X=Br;29) Dimine-metal complex represented by chemical formula IIIb, where R 1 =R 3 =methyl, R 2 =Br, R 4 -R 7 =R 10 =H, R 8 =R 9 =methyl, R 11 =bromomethyl, R 12 =ethyl, M=Ni, Y=O, X=Br;30) Dimine-metal complex represented by chemical formula IIIb, where R 1 =R 3 =F, R 2 =R 4 -R 7 =R 10 =H, R 8 =R 9 =methyl, R 11 =bromomethyl, R 12 =ethyl, M=Ni, Y=O, X=Br;31) Dimine-metal complex represented by chemical formula IIIb, where R 1 =R 3 =Cl, R 2 =R 4 -R 7 =R 10 =H, R 8 =R 9 =methyl, R 11 =bromomethyl, R 12 =ethyl, M=Ni, Y=O, X=Br; and 32) a dimine-metal complex represented by the chemical formula IIIb, where R 1 =R 3 =Br, R 2 =R 4 -R 7 =R 10 =H, R 8 =R 9 =methyl, R 11 =bromomethyl, R 12 = A diimine-metal complex selected from the group consisting of ethyl, M=Ni, Y=O, and X=Br. Claim 15 In claim 1, the dimine-metal complex is a dimine-metal complex represented by the following chemical formula Ic: Chemical formula Ic In the above chemical formula Ic, R 21 -R 24 Each is independently selected from the group consisting of hydrogen, halogen, hydroxyl, C1-C20 hydrocarbyl having or not having substituent Q, and C1-C20 hydrocarbyloxy having or not having substituent Q, and R 21 -R 24 are optionally connected to form a ring or ring system; R1, R2, R 11 , Y, M and X are as defined in Paragraph 1. Claim 16 In claim 15, a dimine-metal complex having one or more of the following features: - in formula A, R 1 -R 5 Each independently hydrogen, halogen, hydroxy, C1-C10 alkyl having or not having substituent Q, C2-C10 alkenyl having or not having substituent Q, C2-C10 alkynyl having or not having substituent Q, C3-C10 cycloalkyl having or not having substituent Q, C1-C10 alkoxy having or not having substituent Q, C2-C10 alkenoxy having or not having substituent Q, C2-C10 alkynoxy having or not having substituent Q, C3-C10 cycloalkoxy having or not having substituent Q, C6-C15 aryl having or not having substituent Q, C6-C15 aryloxy having or not having substituent Q, C7-C15 aralkyl having or not having substituent Q, C7-C15 aralkoxy having or not having substituent Q, and having or not having substituent Q Selected from the group consisting of C7-C15 alkalil and C7-C15 alkaliloxy having or not having substituent Q;- each R 11 is independently a C1-C20 alkyl having or not having substituent Q, or a C1-C10 alkyl having or not having substituent Q, or a C1-C6 alkyl having or not having substituent Q; and- substituent Q is selected from the group consisting of halogen, hydroxy, C1-C6 alkyl, halogenated C1-C6 alkyl, C1-C6 alkoxy, and halogenated C1-C6 alkoxy. Claim 17 In claim 15, the above dimine-metal complex is a dimine-metal complex represented by the following chemical formula IIIc: Chemical formula IIIc. In the above chemical formula IIIc, R 1 -R 10 , R 21 -R 24 Each is independently selected from the group consisting of hydrogen, halogen, hydroxyl, C1-C20 alkyl having or not having substituent Q, C2-C20 alkenyl having or not having substituent Q, C2-C20 alkynyl having or not having substituent Q, C1-C20 alkoxy having or not having substituent Q, C2-C20 alkenoxy having or not having substituent Q, C2-C20 alkynoxy having or not having substituent Q, C6-C20 aryl having or not having substituent Q, C6-C20 aryloxy having or not having substituent Q, C7-C20 aralkyl having or not having substituent Q, C7-C20 aralkoxy having or not having substituent Q, C7-C20 alkaryl having or not having substituent Q, and C7-C20 alkaryloxy having or not having substituent Q, and R 1 -R 10 ... are optionally connected to form a ring or ring system, and R 21 -R 24 are optionally connected to form a ring or ring system;R 11 , Y, M and X are as defined in Paragraph 15. Claim 18 In Paragraph 17, R 1 -R 10 , R 21 -R 24 Each independently hydrogen, halogen, hydroxy, C1-C10 alkyl having or not having substituent Q, C2-C10 alkenyl having or not having substituent Q, C2-C10 alkynyl having or not having substituent Q, C3-C10 cycloalkyl having or not having substituent Q, C1-C10 alkoxy having or not having substituent Q, C2-C10 alkenoxy having or not having substituent Q, C2-C10 alkynoxy having or not having substituent Q, C3-C10 cycloalkoxy having or not having substituent Q, C6-C15 aryl having or not having substituent Q, C6-C15 aryloxy having or not having substituent Q, C7-C15 aralkyl having or not having substituent Q, C7-C15 aralkoxy having or not having substituent Q, and having or not having substituent Q Selected from the group consisting of C7-C15 alkalil and C7-C15 alkaliloxy having or not having substituent Q; or R 1 -R 10 , R 21 -R 24 A diimine-metal complex, each independently selected from the group consisting of hydrogen, C1-C10 alkyl, halogenated C1-C10 alkyl, C1-C10 alkoxy, halogenated C1-C10 alkoxy, and halogen, or selected from the group consisting of hydrogen, C1-C6 alkyl, halogenated C1-C6 alkyl, C1-C6 alkoxy, halogenated C1-C6 alkoxy, and halogen. Claim 19 In paragraph 17, 1) a complex represented by the chemical formula IIIc, where R 1 =R 3 =R 4 =R 6 =isopropyl, R 2 =R 5 =R 7 -R 10 =R 21 =R 22 =R 23 =R 24 =H, R 11 =ethyl, M=Ni, Y=O, X=Br;2) A complex represented by the chemical formula IIIc, where R 1 =R 3 =R 4 =R 6 =ethyl, R 2 =R 5 =R 7 -R 10 =R 21 =R 22 =R 23 =R 24 =H, R 11 =ethyl, M=Ni, Y=O, X=Br;3) A complex represented by the chemical formula IIIc, where R 1 =R 3 =R 4 =R 6 =methyl, R 2 =R 5 =R 7 - R 10 =R 21 =R 22 =R 23 =R 24 =H, R 11 =ethyl, M=Ni, Y=O, X=Br;4) A complex represented by the chemical formula IIIc, where R 1 -R 6 =methyl, R 7 -R 10 =R 21 =R 22 =R 23 =R 24 =H, R 11 =ethyl, M=Ni, Y=O, X=Br; 5) A complex represented by the chemical formula IIIc, where R 1 =R 3 =R 4 =R 6 =Br, R 2 =R 5 =R 7 -R 10 =R 21 =R 22 =R 23 =R 24 =H, R 11 =ethyl, M=Ni, Y=O, X=Br;6) A complex represented by the chemical formula IIIc, where R 1 =R 3 =R 4 =R 6 =Cl, R 2 =R 5 =R 7 -R 10 =R 21 =R 22 =R 23 =R 24 =H, R 11 =ethyl, M=Ni, Y=O, X=Br;7) A complex represented by the chemical formula IIIc, where R 1 =R 3 =R 4 =R 6 =F, R 2 =R 5 =R 7 -R 10 =R 21 =R 22 =R 23 =R 24 =H, R 11 =ethyl, M=Ni, Y=O, X=Br;8) A complex represented by the chemical formula IIIc, where R 1 =R 3 =R 4 =R 6 =isopropyl, R 2 =R 5 =R 7 -R 10 =R 21 =R 22 =R 23 =R 24 =H, R 11 =Isobutyl, M=Ni, Y=O, X=Br;9) A complex represented by the chemical formula IIIc, where R 1 =R 3 =R 4 =R 6 =ethyl, R 2 =R 5 =R 7 -R 10 =R 21 =R 22 =R 23 =R 24 =H, R 11 =isobutyl, M=Ni, Y=O, X=Br;10) A complex represented by the chemical formula IIIc, where R 1 =R 3 =R 4 =R 6 =methyl, R 2 =R 5 =R 7 -R 10 =R 21 =R 22 =R 23 =R 24 =H, R 11 =isobutyl, M=Ni, Y=O, X=Br;11) A complex represented by the chemical formula IIIc, where R 1 -R 6 =methyl, R 7 -R 10 =R 21 =R 22 =R 23 =R 24 =H, R 11 =isobutyl, M=Ni, Y=O, X=Br;12) A complex represented by the chemical formula IIIc, where R 1 =R 3 =R 4 =R 6 =Br, R 2 =R 5 =R 7 - R 10 =R 21 =R 22 =R 23 =R 24 =H, R 11 =isobutyl, M=Ni, Y=O, X=Br;13) A complex represented by the chemical formula IIIc, where R 1 =R 3 =R 4 =R 6 =Cl, R 2 =R 5 =R 7 -R 10 =R 21 =R 22 =R 23 =R 24 =H, R 11 =isobutyl, M=Ni, Y=O, X=Br;14) A complex represented by the chemical formula IIIc, where R 1 =R 3 =R 4 =R 6 =F, R 2 =R 5 =R 7 -R 10 =R 21 =R 22 =R 23 =R 24 =H, R 11 =isobutyl, M=Ni, Y=O, X=Br;15) A complex represented by the chemical formula IIIc, where R 1 =R 3 =R 4 =R 6 =isopropyl, R 2 =R 5 =R 7 -R 10 =R 22 =H, R 21 =tert-butyl, R 23 =R 24 =H, R 11 =ethyl, M=Ni, Y=O, X=Br;16) A complex represented by the chemical formula IIIc, where R 1 =R 3 =R 4 =R 6 =ethyl, R 2 =R 5 =R 7 -R 10 =R 22 =H, R 21 =tert-butyl, R 23 =R 24 =H, R 11 =ethyl, M=Ni, Y=O, X=Br;17) A complex represented by the chemical formula IIIc, where R 1 =R 3 =R 4 =R 6 =methyl, R 2 =R 5 =R 7 -R 10 =R 22 =H, R 21 =tert-butyl, R 23 =R 24 =H, R 11 =ethyl, M=Ni, Y=O, X=Br;18) A complex represented by the chemical formula IIIc, where R 1 -R 6 =methyl, R 7 -R 10 =R 22 =H, R 21 =tert-butyl, R 23 =R 24 =H, R 11 =ethyl, M=Ni, Y=O, X=Br;19) A complex represented by the chemical formula IIIc, where R 1 =R 3 =R 4 =R 6 =Br, R 2 =R 5 =R 7 -R 10 =R 22 =H, R 21 =tert-butyl, R 23 =R 24 =H, R 11 =ethyl, M=Ni, Y=O, X=Br;20) A complex represented by the chemical formula IIIc, where R 1 =R 3 =R 4 =R 6 =Cl, R 2 =R 5 =R 7 -R 10 =R 22 =H, R 21 =tert-butyl, R 23 =R 24 =H, R 11 =ethyl, M=Ni, Y=O, X=Br;21) A complex represented by the chemical formula IIIc, where R 1 =R 3 =R 4 =R 6 =F, R 2 =R 5 =R 7 -R 10 =R 22 =H, R 21 =tert-butyl, R 23 =R 24 =H, R 11 =ethyl, M=Ni, Y=O, X=Br;22) A complex represented by the chemical formula IIIc, where R 1 =R 3 =R 4 =R 6 =isopropyl, R 2 =R 5 =R 7 -R 10 =R 22 =H, R 21 =tert-butyl, R 23 =R 24 =H, R 11 =isobutyl, M=Ni, Y=O, X=Br;23) A complex represented by the chemical formula IIIc, where R 1 =R 3 =R 4 =R 6 =ethyl, R 2 =R 5 =R 7 -R 10 =R 22 =H, R 21 =tert-butyl, R 23 =R 24 =H, R 11 =isobutyl, M=Ni, Y=O, X=Br;24) A complex represented by the chemical formula IIIc, where R 1 =R 3 =R 4 =R 6 =methyl, R 2 =R 5 =R 7 -R 10 =R 22 =H, R 21 =tert-butyl, R 23 =R 24 =H, R 11 =isobutyl, M=Ni, Y=O, X=Br;25) A complex represented by the chemical formula IIIc, where R 1 -R 6 =methyl, R 7 -R 10 =R 22 =H, R 21 =tert-butyl, R 23 =R 24 =H, R 11 =isobutyl, M=Ni, Y=O, X=Br;26) A complex represented by the chemical formula IIIc, where R 1 =R 3 =R 4 =R 6 =Br, R 2 =R 5 =R 7 -R 10 =R 22 =H, R 21 =tert-butyl, R 23 =R 24 =H, R 11 =isobutyl, M=Ni, Y=O, X=Br;27) A complex represented by the chemical formula IIIc, where R 1 =R 3 =R 4 =R 6 =Cl, R 2 =R 5 =R 7 -R 10 =R 22 =H, R 21 =tert-butyl, R 23 =R 24 =H, R 11 =isobutyl, M=Ni, Y=O, X=Br;28) A complex represented by the chemical formula IIIc, where R 1 =R 3 =R 4 =R 6 =F, R 2 =R 5 =R 7 -R 10 =R 22 =H, R 21 =tert-butyl, R 23 =R 24 =H, R 11 =Isobutyl, M=Ni, Y=O, X=Br; (IIIc')29) A complex represented by the chemical formula (IIIc'), where R 1 =R 3 =R 4 =R 6 =isopropyl, R 2 =R 5 =R 7 -R 10 =R 31 =R 32 =H, R 11 =ethyl, M=Ni, Y=O, X=Br;30) A complex represented by the chemical formula (IIIc'), where R 1 =R 3 =R 4 =R 6 =ethyl, R 2 =R 5 =R 7 -R 10 =R 31 =R 32 =H, R 11 =ethyl, M=Ni, Y=O, X=Br;31) A complex represented by the chemical formula (IIIc'), where R 1 =R 3 =R 4 =R 6 =methyl, R 2 =R 5 =R 7 -R 10 =R 31 =R 32 =H, R 11 =ethyl, M=Ni, Y=O, X=Br;32) A complex represented by the chemical formula (IIIc'), where R 1 -R 6 =methyl, R 7 -R 10 =R 31 =R 32 =H, R 11 =ethyl, M=Ni, Y=O, X=Br;33) A complex represented by the chemical formula (IIIc'), where R 1 =R 3 =R 4 =R 6 =Br, R 2 =R 5 =R 7 -R 10 =R 31 =R 32 =H, R 11 =ethyl, M=Ni, Y=O, X=Br;34) A complex represented by the chemical formula (IIIc'), where R 1 =R 3 =R 4 =R 6 =Cl, R 2 =R 5 =R 7 -R 10 =R 31 =R 32 =H, R 11 =ethyl, M=Ni, Y=O, X=Br;35) A complex represented by the chemical formula (IIIc'), where R 1 =R 3 =R 4 =R 6 =F, R 2 =R 5 =R 7 -R 10 =R 31 =R 32 =H, R 11 =ethyl, M=Ni, Y=O, X=Br;36) A complex represented by the chemical formula (IIIc'), where R 1 =R 3 =R 4 =R 6 =isopropyl, R 2 =R 5 =R 7 -R 10 =R 31 =R 32 =H, R 11 =isobutyl, M=Ni, Y=O, X=Br;37) A complex represented by the chemical formula (IIIc'), where R 1 =R 3 =R 4 =R 6 =ethyl, R 2 =R 5 =R 7 -R 10 =R 31 =R 32 =H, R 11 =isobutyl, M=Ni, Y=O, X=Br;38) A complex represented by the chemical formula (IIIc'), where R 1 =R 3 =R 4 =R 6 =methyl, R 2 =R 5 =R 7 -R 10 =R 31 =R 32 =H, R 11 =isobutyl, M=Ni, Y=O, X=Br;39) A complex represented by the chemical formula (IIIc'), where R 1 -R 6 =methyl, R 7 -R 10 =R 31 =R 32 =H, R 11 =isobutyl, M=Ni, Y=O, X=Br;40) A complex represented by the chemical formula (IIIc'), where R 1 =R 3 =R 4 =R 6 =Br, R 2 =R 5 =R 7 -R 10 =R 31 =R 32 =H, R 11 =isobutyl, M=Ni, Y=O, X=Br;41) A complex represented by the chemical formula (IIIc'), where R 1 =R 3 =R 4 =R 6 =Cl, R 2 =R 5 =R 7 -R 10 =R 31 =R 32 =H, R 11 =isobutyl, M=Ni, Y=O, X=Br;42) A complex represented by the chemical formula (IIIc'), where R 1 =R 3 =R 4 =R 6 =F, R 2 =R 5 =R 7 -R 10 =R 31 =R 32 =H, R 11 =isobutyl, M=Ni, Y=O, X=Br;43) A complex represented by the chemical formula (IIIc'), where R 1 =R 3 =R 4 =R 6 =isopropyl, R 2 =R 5 =R 7 -R 10 =HR 31 =R 32 =R 11 =ethyl, M=Ni, Y=O, X=Br;44) A complex represented by the chemical formula (IIIc'), where R 1 =R 3 =R 4 =R 6 =ethyl, R 2 =R 5 =R 7 -R 10 =H, R 31 =R 32 =R 11 =ethyl, M=Ni, Y=O, X=Br;45) A complex represented by the chemical formula (IIIc'), where R 1 =R 3 =R 4 =R 6 =methyl, R 2 =R 5 =R 7 -R 10 =H, R 31 =R 32 =R 11 =ethyl, M=Ni, Y=O, X=Br;46) A complex represented by the chemical formula (IIIc'), where R 1 -R 6 =methyl, R 7 -R 10 =H, R 31 =R 32 =R 11 =ethyl, M=Ni, Y=O, X=Br;47) A complex represented by the chemical formula (IIIc'), where R 1 =R 3 =R 4 =R 6 =Br, R 2 =R 5 =R 7 -R 10 =H, R 31 =R 32 =R 11 =ethyl, M=Ni, Y=O, X=Br;48) A complex represented by the chemical formula (IIIc'), where R 1 =R 3 =R 4 =R 6 =Cl, R 2 =R 5 =R 7 -R 10 =H, R 31 =R 32 =R 11 =ethyl, M=Ni, Y=O, X=Br;49) A complex represented by the chemical formula (IIIc'), where R 1 =R 3 =R 4 =R 6 =F, R 2 =R 5 =R 7 -R 10 =H, R 31 =R 32 =R 11 =ethyl, M=Ni, Y=O, X=Br; 50) A complex represented by the chemical formula (IIIc'), where R 1 =R 3 =R 4 =R 6 =isopropyl, R 2 =R 5 =R 7 -R 10 =H, R 31 =R 32 =R 11 =ethyl, M=Ni, Y=O, X=Br;51) A complex represented by the chemical formula (IIIc'), where R 1 =R 3 =R 4 =R 6 =ethyl, R 2 =R 5 =R 7 -R 10 =H, R 31 =R 32 =ethyl, R 11 =isobutyl, M=Ni, Y=O, X=Br;52) A complex represented by the chemical formula (IIIc'), where R 1 =R 3 =R 4 =R 6 =methyl, R 2 =R 5 =R 7 -R 10 =H, R 31 =R 32 =ethyl, R 11 =isobutyl, M=Ni, Y=O, X=Br;53) A complex represented by the chemical formula (IIIc'), where R 1 -R 6 =methyl, R 7 -R 10 =H, R 31 =R 32 =ethyl, R 11 =isobutyl, M=Ni, Y=O, X=Br;54) A complex represented by the chemical formula (IIIc'), where R 1 =R 3 =R 4 =R 6 =Br, R 2 =R 5 =R 7 -R 10 =H, R 31 =R 32 =ethyl, R 11 =isobutyl, M=Ni, Y=O, X=Br;55) A complex represented by the chemical formula (IIIc'), where R 1 =R 3 =R 4 =R 6 =Cl, R 2 =R 5 =R 7 -R 10 =H, R 31 =R 32 =ethyl, R 11 =isobutyl, M=Ni, Y=O, X=Br; and 56) a complex represented by the chemical formula (IIIc'), where R 1 =R 3 =R 4 =R 6 =F, R 2 =R 5 =R 7 -R 10 =H, R 31 =R 32 =ethyl, R 11 = A diimine-metal complex selected from the group consisting of isobutyl, M=Ni, Y=O, and X=Br. Claim 20 A dimine compound represented by the following chemical formula IV, MX n and R 11 A method for preparing a dimine-metal complex according to claim 1, comprising step 1) of reacting with YH to produce a dimine-metal complex represented by the following chemical formula I: Chemical Formula IV Chemical Formula I In the above Chemical Formula IV, R1, R2, R3 and R4 have the same meaning as defined for Chemical Formula I of Claim 1; MX n In this, M and X have the same meaning as defined for the chemical formula I of claim 1, where n is the number of X satisfying the valence state of M; and R 11 Y and R in YH 11 has the same meaning as defined for Chemical Formula I of Article 1. Claim 21 A method for preparing a diimine-metal complex according to claim 20, wherein the reaction of step 1) is carried out in an organic solvent, and the organic solvent is a halogenated alkane, or the organic solvent is selected from the group consisting of dichloromethane, chloroform, 1,2-dichloroethane and mixtures thereof. Claim 22 A diimine-metal complex for use in olefin polymerization, in any one of claims 1 to 19. Claim 23 A catalyst for olefin polymerization comprising a diimine-metal complex according to any one of claims 1 to 19, a co-catalyst, and a chain transfer agent. Claim 24 An olefin polymerization method comprising carrying out an olefin polymerization reaction in the presence of a diimine-metal complex according to any one of claims 1 to 19, wherein the temperature for the polymerization reaction is in the range of -78 ℃ to 200 ℃ or -20 ℃ to 150 ℃, and the polymerization pressure is in the range of 0.01 to 10.0 MPa or 0.01 to 2.0 MPa. Claim 25 An olefin polymerization method comprising carrying out an olefin polymerization reaction in the presence of a catalyst according to claim 23, wherein the temperature for the polymerization reaction is in the range of -78 ℃ to 200 ℃ or -20 ℃ to 150 ℃, and the polymerization pressure is in the range of 0.01 to 10.0 MPa or 0.01 to 2.0 MPa.

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